JP6171923B2 - Curable resin composition, cured film, light emitting element, wavelength conversion film, and method for forming light emitting layer - Google Patents

Description

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

  Extremely small particles (dots) formed to confine electrons are called quantum dots and have recently attracted attention. The size of one quantum dot is several nanometers to several tens of nanometers in diameter, and is composed of about 10,000 atoms.

  When quantum dots are dispersed in a semiconductor thin film of a solar cell panel, energy conversion efficiency can be greatly improved, so application to solar cells has been studied (for example, see Patent Document 1). .) In addition, by changing the size of the quantum dots (changing the band gap), it is possible to change the color (emission wavelength) of the emitted fluorescence (wavelength conversion), so fluorescent probes in bio research (see Non-Patent Document 1) And application to a display element as a wavelength conversion material (for example, see Patent Document 2 and Patent Document 3).

JP 2006-216560 A JP 2008-112154 A JP 2009-251129 A

Shintaka, “Semiconductor quantum dots, their synthesis and application to life science,” Production and Technology, Vol. 63, No. 2, 2011, p58-p65

  As shown in Examples of Non-Patent Document 1 and Patent Document 1, typical quantum dots are semiconductors made of II-V semiconductors such as CdSe (cadmium selenide), CdTe (cadmium telluride), and PbS. It is a quantum dot.

  However, for example, lead (Pb), which is the main component, is a material well known for its concern for toxicity. Further, cadmium (Cd) and its compounds are extremely toxic even at low concentrations, and are materials for which renal dysfunction and carcinogenicity are a concern. Therefore, there is a demand for the formation of semiconductor quantum dots made of a safer material.

  In addition, when semiconductor quantum dots are to be applied to a solar cell panel, a display of a display element, or the like, formation of a film or a layer composed of semiconductor quantum dots in a particle form may be required in order to utilize the fluorescence emission. That is, the formation of a wavelength conversion film (wavelength conversion film) or a light emitting layer that exhibits fluorescence may be required.

  As a method for forming a light-emitting layer using semiconductor quantum dots in the form of particles, for example, as shown in the Examples of Patent Document 1 and Patent Document 2, a layer made of semiconductor quantum dots directly on an appropriate substrate A method of forming is known. However, in such a formation method, the stability of the obtained light emitting layer is poor. In particular, there is concern about the binding property 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 a particle form in a resin material has been proposed. However, a method for forming a layer or a film together with a resin while using semiconductor quantum dots and stably maintaining the fluorescence characteristics as the semiconductor quantum dots has not been sufficiently studied.

  Therefore, there is a need for a technique for using a semiconductor quantum dot together with a resin material, forming a semiconductor quantum dot layer or film, and forming a highly reliable light-emitting layer or wavelength conversion film. In particular, there is a demand for a resin material that is used together with semiconductor quantum dots and that is suitable for forming a light-emitting layer or a wavelength conversion film composed of a semiconductor quantum dot and a resin.

  In that case, such a resin material is particularly suitable for a semiconductor quantum dot made of a safe material, and is desirably suitable for forming a light emitting layer or a wavelength conversion film. And it is preferable that the resin material protects the dispersed semiconductor quantum dots in the formation of the light emitting layer and the wavelength conversion film, suppresses the deterioration of the fluorescence characteristics, and further improves the reliability.

In addition, it is preferable that the light emitting layer and the wavelength conversion film made of the semiconductor quantum dots and the resin can be easily formed and have high productivity. That is, for the formation of such a light emitting layer and a wavelength conversion film, it is preferable that a simple forming method such as coating can be used. And it is preferable that the light emitting layer and the 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, there is a demand for a resin composition that is prepared containing a semiconductor quantum dot and a resin component and that can form a light-emitting layer or a wavelength conversion film by forming a cured film by using a method such as coating.

  Further, the resin composition preferably has excellent patterning properties. That is, it is preferable that patterning is possible so that the resin composition which forms a light emitting layer and a wavelength conversion film can be used suitably for the structure of light emitting elements, such as a light emitting display element. In that case, the formation of the patterned light-emitting layer and wavelength conversion film can be performed, for example, by photolithography, and can be easily realized.

  Therefore, there is a need for a radiation-sensitive curable resin composition that has excellent radiation sensitivity and can easily form a patterned light-emitting layer and wavelength conversion film using a known patterning method such as a photolithography method. ing.

  The present invention has been made in view of the above problems. That is, an object of the present invention is to provide a curable resin composition that includes a semiconductor quantum dot and can easily form a highly reliable cured film having excellent fluorescence characteristics.

  Another object of the present invention is to provide a cured film that is formed using a curable resin composition containing semiconductor quantum dots and has excellent fluorescence characteristics and high reliability.

  Another object of the present invention is to provide a light-emitting element formed using a curable resin composition containing semiconductor quantum dots and having a light-emitting layer having excellent fluorescence characteristics and reliability.

  Another object of the present invention is to provide a wavelength conversion film that is formed using a curable resin composition containing semiconductor quantum dots, has excellent fluorescence characteristics, and has high reliability.

  Furthermore, 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.

The first aspect of the present invention is:
[X] alkali-soluble resin,
[Y] semiconductor quantum dots,
[Z] polyfunctional acrylate,
The present invention relates to a curable resin composition comprising [V] a chain transfer agent and [W] a radiation-sensitive polymerization initiator.

  In the first aspect of the present invention, the [X] alkali-soluble resin is preferably a polymer containing a structural unit having (X1) an aromatic ring and a structural unit having (X2) (meth) acryloyloxy group.

  1st aspect of this invention WHEREIN: It is preferable that content of the structural unit which has (X1) aromatic ring in [X] alkali-soluble resin is 20 mol%-90 mol% of the whole [X] polymer.

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

In the first embodiment of the present invention, the [Y] semiconductor quantum dot comprises an InP / ZnS compound, a CuInS ₂ / ZnS compound, an AgInS ₂ compound, a (ZnS / AgInS ₂ ) solid solution / ZnS compound, a Zn-doped AgInS ₂ compound, and a Si It is preferably at least one selected from the group consisting of compounds.

  In the first aspect of the present invention, the [V] chain transfer agent preferably contains a compound having a mercapto group.

  The second aspect of the present invention relates to a cured film characterized by being formed using the curable resin composition of the first aspect of the present invention.

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

  4th aspect of this invention is related with the wavelength conversion film formed using the curable resin composition of 1st aspect of this invention.

A fifth aspect of the present invention is a method for forming a light emitting layer of a light emitting element,
(1) The process of forming the coating film of the curable resin composition of the 1st aspect of this invention on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) A step of developing the coating film irradiated with radiation in the step (2), and (4) a step of heating the coating film developed in the step (3). About.

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

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

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

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

  Furthermore, 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.

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 which illustrates typically 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 and board | substrate explaining the hardening process in formation of the cured film of 2nd Embodiment of this invention. It is sectional drawing which shows typically the light emitting display element of 3rd Embodiment of this invention.

  The curable resin composition of the present invention includes [X] alkali-soluble resin (hereinafter also simply referred to as [X] component), [Y] semiconductor quantum dots (hereinafter also simply referred to as [Y] component), and [Z. ] Polyfunctional acrylate (hereinafter also referred to simply as [Z] component), [V] chain transfer agent (hereinafter also referred to simply as [V] component), [W] radiation sensitive polymerization initiator (hereinafter referred to simply as [[ W] component)) is a curable resin composition.

  The curable resin composition of the present invention contains [X] alkali-soluble resin and [Y] semiconductor quantum dots, and can form a layer or film made of a resin material including the semiconductor quantum dots. The curable resin composition of the present invention further contains a [V] chain transfer agent and [Z] polyfunctional acrylate, and promotes crosslinking of the resin component to form a layer or film containing semiconductor quantum dots. be able to. That is, the layer or film formed from the curable resin composition of the present invention is improved in strength by crosslinking of the resin component, protects the semiconductor quantum dots contained, and suppresses deterioration of characteristics during formation, The reliability can be improved.

  Moreover, the curable resin composition of this invention contains a [W] radiation sensitive polymerization initiator, and can have radiation sensitivity. Therefore, the curable resin composition of the present invention can be patterned using, for example, a photolithography method based on its radiation sensitivity.

  In the present invention, “radiation” irradiated upon exposure includes visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams, and the like.

  Also, in the photolithography method, a so-called resist composition is applied to the surface of a substrate to be processed or processed to form a resist film, and a predetermined resist pattern is exposed by irradiating light or an electron beam. An exposure process for forming a resist pattern latent image, a heating process as necessary, a development process for developing the resist pattern to form a desired fine pattern, and a process such as etching the substrate using the fine pattern as a mask The process etc. which perform are included.

  The curable resin composition of the present invention is patterned when necessary to form the cured film of the present invention. The cured film of the present invention is constituted by including [Y] semiconductor quantum dots in a resin reinforced by crosslinking.

  The cured film of the present invention has a fluorescence emission (wavelength conversion) function based on [Y] semiconductor quantum dots. 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 the present 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 the present invention described later.

  Hereinafter, the curable resin composition, the cured film, the light emitting element, the wavelength conversion film, and the method for forming the light emitting layer of the present invention will be described.

Embodiment 1 FIG.
<Curable resin composition>
As described above, the curable resin composition of the first embodiment of the present invention includes [X] alkali-soluble resin, [Y] semiconductor quantum dots, [Z] polyfunctional acrylate, [V] chain transfer agent, and [W]. ] Consists of a radiation-sensitive polymerization initiator. [X] The alkali-soluble resin is not limited as long as it is a resin having alkali developability. Hereinafter, the [X] alkali-soluble resin of the curable resin composition is also simply referred to as [X] polymer.

[X] As the polymer, for example, acrylic resin or polyimide can be used. The [X] polymer can be a polymer containing a structural unit having (X1) an aromatic ring and a structural unit having (X2) (meth) acryloyloxy group, among others.
Moreover, the curable resin composition which is embodiment of this invention can contain another arbitrary component, unless the effect of this invention is impaired.

  The curable resin composition of the present invention contains an excellent fluorescent emission (wavelength conversion) function (hereinafter simply referred to as fluorescence or fluorescence characteristics) containing [Y] semiconductor quantum dots by utilizing a method such as coating. It is also possible to form a cured film according to an embodiment of the present invention having high reliability.

  Hereinafter, the components contained in the curable resin composition of the first embodiment of the present invention will be described.

[[X] polymer]
[X] The polymer can be a polymer containing (X1) a structural unit having an aromatic ring and (X2) a structural unit having a (meth) acryloyloxy group, as described above. [X] The polymer is an alkali-soluble resin that is soluble in alkali. Here, in particular, the [X] polymer, which is a polymer containing a structural unit having (X1) an aromatic ring and a structural unit having (X2) (meth) acryloyloxy group, will be described.

  (X1) The structural unit having an aromatic ring is a structural unit represented by the following formula (1). (X1) By including the structural unit which has an aromatic ring, the heat resistance of the cured film formed using a curable resin composition can be improved.

In the above formula ^{(1), R 21} represents an alkyl group having 1 to 12 carbon atoms, a hydroxyl group, an alkoxyl group having 1 to 12 carbon atoms, a halogen. R ²² represents a single bond, a methylene group, or an alkylene group having 2 to 6 carbon atoms. R ²³ represents a single bond or an ester bond. R ²⁴ represents a hydrogen atom or a methyl group.

  (X1) Specific polymerizable compounds for forming a structural unit having an aromatic ring include the following.

Styrene, p-hydroxystyrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-chlorostyrene, p-methoxystyrene, p- (t-butoxy) styrene;
Examples include phenyl acrylate, phenyl methacrylate, 4-hydroxyphenyl acrylate, 4-hydroxyphenyl methacrylate, benzyl acrylate, benzyl methacrylate, phenethyl acrylate, phenethyl methacrylate, and the like.

  Of these, styrene, benzyl acrylate, and benzyl methacrylate are particularly desirable from the viewpoint of polymerizability.

  [X] The content of the structural unit having an aromatic ring (X1) in the polymer is preferably 20 mol% to 90 mol%, more preferably 50 mol% to 80 mol%, of all the components of the [X] polymer. It is.

  When the content is less than 20 mol%, it is difficult to control the strength of the obtained cured film sufficiently, and the heat resistance is not sufficient. On the other hand, when the content exceeds 90 mol%, a development residue is likely to occur during patterning, causing development failure during development.

  [X] The structural unit having a (X2) (meth) acryloyloxy group of the polymer is obtained by reacting a carboxyl group in the polymer with a (meth) acrylic acid ester having an epoxy group. The structural unit having a (meth) acryloyloxy group after the reaction is preferably a structural unit represented by the following formula (2).

In the above formula (2), R ¹⁰ and R ¹¹ are each independently a hydrogen atom or a methyl group. c is an integer of 1-6. R ¹² is a divalent group represented by the following formula (3-1) or the following formula (3-2).

In the above formula ^{(3-1), R 13} is a hydrogen atom or a methyl group. In the above formula (3-1) and the above formula (3-2), * represents a site bonded to an oxygen atom.

For the structural unit represented by the formula (2), for example, when a compound having a carboxyl group is reacted with a compound such as glycidyl methacrylate or 2-methylglycidyl methacrylate, R in the formula (2) ¹² becomes Formula (3-1). On the other hand, when a copolymer such as 3,4-epoxycyclohexylmethyl methacrylate is reacted with a copolymer having a carboxyl group, R ¹² in the formula (2) becomes the formula (3-2).

  In the reaction of the carboxyl group in the polymer described above with an unsaturated compound such as a (meth) acrylic acid ester having an epoxy group, a polymer containing a polymerization inhibitor is preferably contained in the presence of a suitable catalyst as necessary. An unsaturated compound having an epoxy group is added to the combined solution and stirred for a predetermined time under heating. Examples of the catalyst include tetrabutylammonium bromide. Examples of the polymerization inhibitor include p-methoxyphenol. The reaction temperature is preferably 70 ° C to 100 ° C. The reaction time is preferably 8 hours to 12 hours.

[X] The content of the structural unit having (X2) (meth) acryloyloxy group in the polymer is preferably 10 mol% to 70 mol%, and 20 mol% to 50 mol% of all the components of the [X] polymer. It is more preferable that
(X2) When the content of the structural unit having a (meth) acryloyloxy group is less than 10 mol%, the sensitivity of the curable resin composition of the present embodiment to radiation tends to decrease, and the heat resistance of the resulting cured film Sex is not enough. On the other hand, when the content is more than 70 mol%, it causes development failure at the time of development, and development residue tends to occur.

  The carboxyl group in the polymer can be introduced by polymerizing an unsaturated monomer having a carboxyl group shown below. And the structural unit which has a carboxyl group is comprised.

  Examples of such unsaturated monomers include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, and mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids.

  Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like. As an anhydride of unsaturated dicarboxylic acid, the anhydride of the compound illustrated as said dicarboxylic acid etc. are mentioned, for example.

  Examples of mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids include succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl] and the like. It is done.

  Among these, acrylic acid, methacrylic acid, and maleic anhydride are preferable, and acrylic acid, methacrylic acid, and maleic anhydride are more preferable from the viewpoint of copolymerization reactivity, solubility in an alkaline aqueous solution, and availability. These compounds may be used alone or in combination of two or more.

  The usage rate is desirably 5 mol% to 20 mol% higher than the usage rate of the structural unit having the (X2) (meth) acryloyloxy group. This is because, when all of the carboxyl groups are reacted with the (meth) acrylic acid ester having an epoxy group, the developability with respect to an alkaline developer is impaired. Therefore, it is preferably in the range of 5 mol% to 90 mol%, and more preferably in the range of 15 mol% to 70 mol%.

  [X] The polymer comprises (X1) a structural unit having an aromatic ring (hereinafter, also simply referred to as “(X1) structural unit”), (X2) a structural unit having a (meth) acryloyloxy group (hereinafter simply referred to as “X1”). In addition to “(X2) structural unit”) and the above-mentioned structural unit having a carboxyl group (hereinafter referred to as “(X3) structural unit”), the following structural units derived from unsaturated monomers ( Hereinafter, it may be referred to as “(X4) structural unit”.

  Examples of the structural unit (X4) include the following structural units having an oxetanyl group, structural units having an alkyl group, structural units having a maleimide skeleton, and structural units having a tetrahydrofuran skeleton.

As an unsaturated monomer that forms a structural unit having an oxetanyl group, for example,
3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -2-phenyloxetane, 3- (2-acryloyloxyethyl) oxetane, 3- (2-acryloyloxyethyl) -2-ethyloxetane, 3- (2-acryloyloxyethyl) -3-ethyloxetane, 3- (2-acryloyloxyethyl) -2 -Acrylic esters such as phenyloxetane;
3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyloxyethyl) -2-ethyloxetane, 3- (2-methacryloyloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) -2 -Methacrylic acid esters such as phenyloxetane and 3- (2-methacryloyloxyethyl) -2,2-difluorooxetane.

(X4) Examples of the unsaturated monomer that forms a structural unit having an alkyl group that is a structural unit include a methacrylic acid chain alkyl ester, a methacrylic acid cyclic alkyl ester, and the like.
Examples of the chain alkyl ester of methacrylic acid include, for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n methacrylate. -Lauryl, tridecyl methacrylate, n-stearyl methacrylate and the like.
Examples of the cyclic alkyl ester of methacrylic acid include, for example, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, and tricyclomethacrylate [5. 2.1.0 ^2,6 ] decan-8-yloxyethyl, isobornyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, acrylic acid 2 -Ethylhexyl, isodecyl acrylate, n-lauryl acrylate, tridecyl acrylate, n-stearyl acrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricycloacrylate [5.2.1.0 ^2,6 ] Decan-8-yl, trisic acrylate [5.2.1.0 ^2,6] decan-8-yl oxy ethyl, and the like isobornyl acrylate.

(X4) Examples of the unsaturated monomer that forms a structural unit having a maleimide skeleton as a structural unit include a maleimide compound.
Examples of maleimide compounds include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) maleimide, N-succinimidyl-3-maleimidobenzoate N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide and the like.

  (X4) Examples of the unsaturated monomer that forms a structural unit containing a tetrahydrofuran skeleton which is a structural unit include methacrylic acid tetrahydrofurfuryl, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, and 3- (meth). And acryloyloxytetrahydrofuran-2-one.

(X4) Among unsaturated monomers constituting the structural unit, methyl methacrylate, t-butyl methacrylate, n-lauryl methacrylate, tricyclomethacrylate [5.2.1.0 ^2,6 ] decane-8 -Il, acrylate-2-methylcyclohexyl, N-phenylmaleimide, N-cyclohexylmaleimide, and tetrahydrofurfuryl methacrylate are preferred from the viewpoints of copolymerization reactivity and solubility in an aqueous alkali solution.

  These compounds may be used alone or in combination of two or more for the formation of the (X4) structural unit. The use ratio is preferably 10% by mass to 80% by mass based on the total of (X1) structural unit, (X2) structural unit, (X3) structural unit, and (X4) structural unit.

  [X] The polymer is, for example, a compound for forming the (X1) constituent unit (hereinafter also referred to as “(X1) compound”) and (X2) constituent unit in the presence of a polymerization initiator in a solvent. (Hereinafter also referred to as “(X2) compound”) (compound for forming an arbitrary (X3) structural unit (hereinafter also referred to as “(X3) compound”) compound and (X4) ) It can be produced by copolymerizing an unsaturated monomer (hereinafter also referred to as “(X4) compound”) for forming a structural unit.

  [X] Solvents used in the polymerization reaction for producing the polymer include, for example, alcohol, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, dipropylene glycol dialkyl ether, propylene glycol mono Examples include alkyl ether, propylene glycol alkyl ether acetate, propylene glycol monoalkyl ether propionate, methyl-3-methoxypropionate, ketone, ester and the like.

  [X] As the polymerization initiator used in the polymerization reaction for producing the polymer, those generally known as radical polymerization initiators can be used. Examples of the radical polymerization initiator include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- (4 Azo compounds such as -methoxy-2,4-dimethylvaleronitrile).

  [X] In the polymerization reaction for producing the polymer, a molecular weight modifier can be used for the purpose of adjusting the molecular weight.

  Examples of the molecular weight modifier include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, and thioglycolic acid; Examples thereof include xanthogens such as dimethylxanthogen sulfide and diisopropylxanthogen disulfide; terpinolene and α-methylstyrene dimer.

  [X] The weight average molecular weight (Mw) of the polymer is preferably 1000 to 30000, more preferably 5000 to 20000. [X] By making Mw of a polymer into the said range, the sensitivity with respect to the radiation and developability of the curable resin composition of this embodiment can be improved. The Mw and number average molecular weight (Mn) of the [X] polymer can be measured by gel permeation chromatography (GPC).

[[Y] Semiconductor quantum dot]
The [Y] semiconductor quantum dot, which is a component of the curable resin composition of the first embodiment of the present invention, does not contain Cd or Pb as a constituent component, for example, contains In (indium) or Si (silicon) as a constituent component. A semiconductor quantum dot composed of a safe material.

  [Y] The semiconductor quantum dot is at least two elements selected from the group consisting of group 2 element, group 11 element, group 12 element, group 13 element, group 14 element, group 15 element and group 16 element It is preferable that it is a semiconductor quantum dot which consists of a compound containing this.

  More specifically, elements such as Pb and Cd, which are of great concern for human safety, 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), S (Sulfur), Se (selenium), Te (tellurium), and a semiconductor quantum dot which consists of a compound containing at least 2 or more types of elements chosen from Po (polonium) group are preferable.

  At this time, it is preferable that the [Y] 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.

  [Y] The semiconductor quantum dot is composed of the compound (A) and / or the compound (B) having such fluorescence emission characteristics, so that the wavelength range of 500 nm to 600 nm and / or the wavelength range of 600 nm to 700 nm is obtained. It can have a fluorescence maximum. As a result, the curable resin composition of the present embodiment containing [Y] semiconductor quantum dots forms a cured film suitable for the structure of the light emitting layer of the light emitting element that displays an image using light in the visible range. be able to.

  Furthermore, it is more preferable that the [Y] semiconductor quantum dots contained in the curable resin composition of the present embodiment are semiconductor quantum dots made of a compound containing In as a constituent component. In addition, examples of [Y] semiconductor quantum dots include Si compounds.

  [Y] Si is preferable as the Si compound preferable as the semiconductor quantum dot.

  [Y] By making the component configuration of the semiconductor quantum dots as described above, the curable resin composition of the present embodiment can form a cured film that is safe and has excellent fluorescence characteristics. A wavelength conversion film having a safe and excellent fluorescence characteristic and a light emitting layer of a light emitting element can be formed.

  [Y] semiconductor quantum dots contained in the curable resin composition of this embodiment are at least one selected from a homogeneous structure type composed of one compound and a core-shell structure type composed of two or more compounds. The structure type semiconductor quantum dot is preferable.

  A core-shell structure type [Y] semiconductor quantum dot is formed by forming a core structure with one kind of compound and coating the periphery of the core structure with another compound. For example, by covering the core semiconductor with a semiconductor having a larger band gap, excitons (electron-hole pairs) generated by photoexcitation are confined in the core. As a result, the probability of non-radiative transition on the surface of the quantum dot is reduced, and the quantum yield of light emission and the stability of the fluorescence characteristics of the [Y] semiconductor quantum dot are improved.

[Y] semiconductor quantum dots contained in the curable resin composition of the present embodiment are InP / ZnS, CuInS ₂ / ZnS, and (ZnS / AgInS ₂ ) solid solution / ZnS and at least one selected from the group consisting of AgInS ₂ and Zn-doped AgInS ₂ which are homogeneous structure type semiconductor quantum dots are preferable.

From the above, the [Y] semiconductor quantum dots contained in the curable resin composition of the present embodiment are InP / ZnS compound, CuInS ₂ / ZnS compound, AgInS ₂ compound, (ZnS / AgInS ₂ ) solid solution / ZnS compound, It is preferably at least one selected from the group of Zn-doped AgInS ₂ compound and Si compound.

  The curable resin composition of the present embodiment containing the [Y] semiconductor quantum dots exemplified above forms a cured film that is safe and has superior fluorescence characteristics, and more excellent fluorescence. A characteristic wavelength conversion film or a light emitting layer of a light emitting element can be formed.

  In addition, the [Y] semiconductor quantum dots contained in the curable resin composition of the present embodiment preferably have an average particle diameter of 0.5 nm to 20 nm, and more preferably 1.0 nm to 10 nm. When the average particle size is less than 0.5 nm, it is difficult to prepare the [Y] semiconductor quantum dots, and even if the preparation is completed, the fluorescence characteristics of the [Y] semiconductor quantum dots may become unstable. is there. [Y] If 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 desirable.

  Moreover, the shape of [Y] semiconductor quantum dot is not specifically limited, For example, spherical shape, rod shape, 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 [Y] semiconductor quantum dot contained in the curable resin composition of 1st Embodiment of this invention, utilizing the well-known method of thermally decomposing an organometallic compound in a coordinating organic solvent. Can do. For core-shell structure type semiconductor quantum dots, after forming a homogeneous core structure by reaction, a precursor for forming a shell on the core surface is added to the reaction system, and the reaction is stopped after the shell formation. And can be obtained by separating from the solvent. A commercially available product can also be used.

  The content of [Y] semiconductor quantum dots in the curable resin composition of the present embodiment is preferably 0.1 parts by mass to 100 parts by mass, more preferably 100 parts by mass with respect to the above-mentioned [X] component. Is 0.2 part by mass to 50 parts by mass. [Y] By setting the content of the semiconductor quantum dots in the above range, a cured film having excellent fluorescence characteristics is formed, and as a result, a wavelength conversion film having excellent fluorescence characteristics and a light emitting layer of the light emitting element are formed. be able to. [Y] When the content of the semiconductor quantum dots is less than 0.1 parts by mass with respect to 100 parts by mass of the [X] component, the desired fluorescent property cannot be obtained in the formed cured film, and the wavelength The light emitting layer of a conversion film or a light emitting element cannot be formed. Moreover, when there are more than 100 mass parts with respect to 100 mass parts of [X] component, stability of the cured film formed will be impaired and the stable wavelength conversion film and the light emitting layer of a light emitting element cannot be formed.

[[Z] polyfunctional acrylate]
The curable resin composition of this embodiment can contain a polymerizable compound having a plurality of (meth) acryloyl groups in the molecule as [Z] polyfunctional acrylate. As one of the functions of this polymerizable compound, when the curable resin composition of the present embodiment is irradiated with light as radiation, it is polymerized to form a high molecular weight or form a crosslinked structure. It is done. By containing such a polymerizable compound, the entire coating film of the curable resin composition can be cured, the strength of the formed cured film can be improved, and the protective function of the contained semiconductor quantum dots can be enhanced. Furthermore, it is possible to improve the contrast between the light irradiated portion and the non-irradiated portion, thereby preventing peeling during development and suppressing the formation of residues.

  Here, “(meth) acryloyl group” means an acryloyl group or a methacryloyl group, and “having a plurality of (meth) acryloyl groups in a molecule” means an acryloyl group present in the molecule. The total of group and methacryloyl group is 2 or more. In that case, the total number of these groups should just be 2 or more, and either an acryloyl group and a methacryloyl group do not need to exist.

  Examples of the polymerizable compound having a plurality of (meth) acryloyl groups in the molecule include the following.

  Examples of the polymerizable compound having two (meth) acryloyl groups in the molecule include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di ( (Meth) acrylate, 1,10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2,4-dimethyl-1,5-pentanediol di (meth) acrylate, butylethylpropanediol (meth) Acrylate, ethoxylated cyclohexanemethanol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, oligoethylene Recall di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 2-ethyl-2-butyl-butanediol di (meth) acrylate, full orange (meth) acrylate, hydroxypivalic acid Neopentyl glycol di (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, bisphenol F polyethoxydi (meth) acrylate, oligopropylene glycol di (meth) acrylate, 2-ethyl-2-butyl-propanediol di (meth) Acrylate, 1,9-nonanediol di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, tricyclodecane di (meth) acrylate, bis (2-hydride) Kishiechiru) isocyanurate di (meth) acrylate.

  Examples of polymerizable compounds having three (meth) acryloyl groups in the molecule include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane alkylene oxide-modified tri (meth) acrylate, penta Erythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, trimethylolpropane tri {(meth) acryloyloxypropyl} ether, glycerin tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri ( (Meth) acrylate, isocyanuric acid alkylene oxide modified tri (meth) acrylate, propionate dipentaerythritol tri (meth) acrylate, tri {(meth) acryloyloxy Chill} isocyanurate, hydroxypivalaldehyde-modified dimethylol propane tri (meth) acrylate, sorbitol tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and ethoxylated glycerin triacrylate.

  Polymerizable compounds having four (meth) acryloyl groups in the molecule include pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and dipentaerythritol tetrapropionate (meth). ) Acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, succinic acid-modified pentaerythritol triacrylate and the like.

  Examples of the polymerizable compound having five (meth) acryloyl groups in the molecule include sorbitol penta (meth) acrylate and dipentaerythritol penta (meth) acrylate.

  Examples of polymerizable compounds having six (meth) acryloyl groups in the molecule include dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene alkylene oxide-modified hexa (meth) acrylate, and caprolactone-modified dipentaerythritol. Examples include hexa (meth) acrylate.

  [Z] The polyfunctional acrylate may be a polymerizable compound having seven or more (meth) acryloyl groups. Moreover, [Z] polyfunctional acrylate may be (meth) acrylates having a hydroxyl group among the above-described polymerizable compounds, and poly (meth) acrylates of ethylene oxide or propylene oxide adducts to these hydroxyl groups. Good. Furthermore, as [Z] polyfunctional acrylate, if it is a compound having two or more (meth) acryloyl groups, oligoester (meth) acrylates, oligoether (meth) acrylates, and oligoepoxy (meth) acrylates Etc. can be used.

  Among these [Z] polyfunctional acrylates, among them, pentaerythritol tri (meth) acrylate, full orange (meth) acrylate, oligoester (meth) acrylate {dendrimer (meth) acrylate} are excellent in polymerizability. More preferred.

  About the commercial item of the polymerizable compound illustrated as [Z] polyfunctional acrylate above, for example, Toronsei Co., Ltd. Aronix (registered trademark) M-400, M-404, M-408, M-450, M -305, M-309, M-310, M-313, M-315, M-321, M-402, M-350, M-360, M-208, M-210, M-215, M-220 M-225, M-233, M-240, M-245, M-260, M-270, M-1100, M-1200, M-1210, M-1310, M-1600, M-221, M -203, TO-924, TO-1270, TO-1231, TO-595, TO-756, TO-1343, TO-902, TO-904, TO-905, TO-1330, TO-1450, TO 1382, KAYARAD (registered trademark) D-310, D-330, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, SR-295 manufactured by Nippon Kayaku Co., Ltd. SR-355, SR-399E, SR-494, SR-9041, SR-368, SR-415, SR-444, SR-454, SR-492, SR-499, SR-502, SR-9020, SR -9035, SR-111, SR-212, SR-213, SR-230, SR-259, SR-268, SR-272, SR-344, SR-349, SR-601, SR-602, SR-610 , SR-9003, PET-30, T-1420, GPO-303, TC-120S, HDDA, NPGDA, TPGD , PEG400DA, MANDA, HX-220, HX-620, R-551, R-712, R-167, R-526, R-551, R-712, R-604, R-684, RP-1040, RP -2040, TMPTA, THE-330, TPA-320, TPA-330, KS-HDDA, KS-TPGDA, KS-TMPTA, Kyoeisha Chemical Co., Ltd. Light Acrylate PE-4A, DPE-6A, DTMP-4A, Osaka Organic Examples include Biscoat # 802 manufactured by Chemical Industry Co., Ltd .; a mixture of tripentaerythritol octaacrylate and tripentaerythritol heptaacrylate.

  As for content of [Z] polyfunctional acrylate in the curable resin composition of this embodiment, 1 mass%-20 mass% are preferable with respect to the whole curable resin composition. Moreover, when the curable resin composition of this embodiment contains an organic solvent, content of [Z] polyfunctional acrylate in curable resin composition is 5 mass% with respect to the sum total of the component except an organic solvent. It is preferable to be within a range of ˜50% by mass or less, and it is more preferable to be within a range of 10% by mass to 40% by mass. [Z] By containing the polyfunctional acrylate in the above range, a cured film having high hardness can be obtained from the curable resin composition.

[[V] chain transfer agent]
The inventor has studied to improve the curing performance in the layer or film of the present invention containing a resin quantum component and containing semiconductor quantum dots, and has studied to improve the protective function of the semiconductor quantum dots. And this inventor discovered that use of a chain transfer agent was effective in order to improve the sclerosis | hardenability of the layer and film | membrane of this invention.

  Therefore, the curable resin composition of this embodiment contains the [V] chain transfer agent which is a [V] component. A chain transfer reaction is a reaction in which radicals of a growing polymer chain move to another molecule in radical polymerization, and a chain transfer agent is an agent that causes a chain transfer reaction. In the layer or film formed from the curable resin composition of the present invention, the crosslinking of the resin component is advanced by the action of the chain transfer agent, and the strength is improved. As a result, in the layer or film of the present invention, the function of protecting the contained semiconductor quantum dots is improved, and the deterioration of the fluorescence characteristics of the semiconductor quantum dots can be suppressed and the reliability can be improved.

  The [V] chain transfer agent contained in the curable resin composition of the present embodiment is not particularly limited as long as it is a compound that functions as a chain transfer agent in a radical polymerization reaction. Examples of the [V] chain transfer agent that is preferably contained in the curable resin composition of the present embodiment include those containing a pyrazole derivative, alkylthiols and the like.

  And as a preferable [V] chain transfer agent, what contains the compound etc. which have a mercapto group (thiol group) etc. can be mentioned, for example, as a more preferable [V] chain transfer agent, it is 2 in 1 molecule. The thing containing the compound etc. which have the above mercapto groups can be mentioned.

  [V] The compound having two or more mercapto groups in one molecule, preferably contained in the chain transfer agent, is not particularly limited as long as it has two or more mercapto groups in one molecule. For example, at least 1 sort (s) chosen from the group which consists of a compound represented by following formula (4) can be mentioned.

In the formula ^{(4), R 31} is a methylene group, an alkylene group having 2 to 10 carbon atoms. However, in these groups, some or all of the hydrogen atoms may be substituted with alkyl groups. Y ¹ is a single bond, —CO— or —O—CO— ^* . However, bond binds to ^{R 31} marked with *. n is an integer of 2-10. A ¹ is an n-valent hydrocarbon group having 2 to 70 carbon atoms which may have one or a plurality of ether bonds, or a group represented by the following formula (5) when n is 3. .

上記式（５）中、Ｒ^３２〜Ｒ^３４は、それぞれ独立してメチレン基または炭素数２〜６のアルキレン基である。「＊」は、それぞれ結合手であることを表す。

In said formula (5), R < ³² > -R < ³⁴ > is a methylene group or a C2-C6 alkylene group each independently. “*” Represents a bond.

  As the compound represented by the above formula (4), typically, an esterified product of mercaptocarboxylic acid and a polyhydric alcohol can be used. Examples of the mercaptocarboxylic acid constituting the esterified product include thioglycolic acid, 3-mercaptopropionic acid, 3-mercaptobutanoic acid, and 3-mercaptopentanoic acid. Examples of the polyhydric alcohol constituting the esterified product include ethylene glycol, propylene glycol, trimethylolpropane, pentaerythritol, tetraethylene glycol, dipentaerythritol, 1,4-butanediol, and pentaerythritol.

  Examples of the compound represented by the above formula (4) include trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), and tetraethylene glycol bis (3-mercaptopropionate). Dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (thioglycolate), 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), Pentaerythritol tetrakis (3-mercaptopentylate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione preferable.

  As the compound having two or more mercapto groups in one molecule of the thiol compound, compounds represented by the following formulas (6) to (8) can also be used.

In the above formula ^{(6), R 41} is an alkylene group of methylene group or 2-20 carbon atoms. ^R42 is a methylene group or a linear or branched alkylene group having 2 to 6 carbon atoms. k is an integer of 1-20.
In the above formula (7), R ^{43 to} R ⁴⁶ are each independently a hydrogen atom, a hydroxyl group or a group represented by the following formula (8). However, at least one of R ^{43 to} R ⁴⁶ is a group represented by the following formula (8).

In the formula ^{(8), R 47} is a methylene group or a linear or branched alkylene group having 2 to 6 carbon atoms.

  [V] As the chain transfer agent, one or more compounds may be mixed and used. As a content rate of the [V] chain transfer agent in the curable resin composition of this embodiment, 0.5 mass part-20 mass parts are preferable with respect to 100 mass parts of [X] polymers, and 1 mass part- 15 parts by mass is more preferable. [V] When the amount of the chain transfer agent used is less than 0.5 parts by weight, the effect of improving the curability cannot be sufficiently obtained. When the amount exceeds 20 parts by weight, the sensitivity becomes too sensitive and the light leaks. There is a possibility that the pattern performance may be lowered by increasing the curability.

[[W] radiation sensitive polymerization initiator]
The curable resin composition of this embodiment contains a [W] radiation-sensitive polymerization initiator together with [Z] polyfunctional acrylate. [W] The radiation-sensitive polymerization initiator is a component that generates an active species that can initiate polymerization of [Z] polyfunctional acrylate in response to radiation. [W] The radiation-sensitive polymerization initiator is, for example, a radical photopolymerization initiator. Examples of such [W] radiation-sensitive polymerization initiators include O-acyloxime compounds, acetophenone compounds, biimidazole compounds, and the like. These compounds may be used alone or in combination of two or more.

  Examples of the O-acyloxime compound described above include 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone-1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) and the like.

  Among these, 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole -3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) or ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) is preferred.

  Examples of acetophenone compounds include α-aminoketone compounds 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, and the like.

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

  As the acetophenone compound, an α-aminoketone compound is preferable, and in particular, 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 are preferred.

  Examples of the biimidazole compound include 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 or 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5 5'-tetraphenyl-1,2'-biimidazole is preferred, of which 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'- Biimidazole is more preferred.

[W] As described above, the radiation-sensitive polymerization initiator can be used alone or in admixture of two or more.
[W] The content of the radiation-sensitive polymerization initiator is preferably 1 part by mass to 40 parts by mass, and more preferably 5 parts by mass to 30 parts by mass with respect to 100 parts by mass of the [X] polymer. [W] By setting the content of the radiation-sensitive polymerization initiator to 1 part by mass to 40 parts by mass, the curable resin composition of the present embodiment has high solvent resistance and high even at a low exposure amount. A cured film having hardness and high adhesion can be formed.

[Optional ingredients]
In addition to the [X] polymer, [Y] semiconductor quantum dot, [Z] polyfunctional acrylate, [V] chain transfer agent and [W] radiation sensitive polymerization initiator, the curable resin composition of the present embodiment, In addition to the organic solvent, other optional components such as a surfactant and an adhesion aid can be contained as necessary within the range not impairing the effects of the present invention. Two or more optional components may be mixed and used. Hereinafter, each component will be described.

[Surfactant]
The surfactant contained in the curable resin composition of this embodiment can be added to improve the applicability of the curable resin composition, reduce coating unevenness, and improve the developability of the radiation irradiated part. . Examples of preferable surfactants include fluorine-based surfactants and silicone-based surfactants.

  Examples of the fluorosurfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl hexyl ether, octa Ethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,2, , 2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether and other fluoroethers; sodium perfluorododecylsulfonate; 1,1,2, 2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexa Fluoroalkanes such as lurodecane; sodium fluoroalkylbenzenesulfonates; fluoroalkyloxyethylene ethers; fluoroalkylammonium iodides; fluoroalkylpolyoxyethylene ethers; perfluoroalkylpolyoxyethanols; perfluoroalkylalkoxylates And fluorine-based alkyl esters.

Commercially available products of these fluorosurfactants include Ftop (registered trademark) EF301, 303, and 352 (manufactured by Shin-Akita Kasei Co., Ltd.), MegaFac (registered trademark) F171, 172, and 173 (DIC Corporation). Manufactured), FLORARD FC430, 431 (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard AG (registered trademark) 710 (manufactured by Asahi Glass Co., Ltd.), Surflon (registered trademark) S-382, SC-101, 102, 103, 104 , 105, 106 (manufactured by AGC Seimi Chemical Co., Ltd.), FTX-218 (manufactured by Neos Co., Ltd.), and the like.
Examples of silicone-based surfactants are commercially available under the trade names SH200-100cs, SH28PA, SH30PA, ST89PA, SH190, SH8400 FLUID (manufactured by Toray Dow Corning Silicone Co., Ltd.), organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.).

  When using a surfactant as an optional component, the content thereof is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the [X] polymer. Part by mass. By making the usage-amount of surfactant into 0.01 mass part-10 mass parts, the applicability | paintability of curable resin composition can be optimized.

[Adhesion aid]
In the curable resin composition of the present embodiment, an insulating material such as silicon, silicon oxide, silicon nitride and other silicon compounds, glass such as silicate and quartz, and metal such as gold, copper and aluminum are insulated. An adhesion aid can be used to improve the adhesion to the film. Examples of such adhesion assistants include functional silane coupling agents. Examples of functional silane coupling agents include silane coupling agents having reactive substituents such as carboxyl groups, methacryloyl groups, isocyanate groups, epoxy groups (preferably oxiranyl groups), thiol groups, and the like.

  Specific examples of functional silane coupling agents include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxy Examples include propyltrimethoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. . Among these, γ-glycidoxypropylalkyldialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane are preferable.

  In the curable resin composition of the present embodiment, such an adhesion assistant is preferably 0.5 parts by mass to 20 parts by mass, more preferably 1 part by mass, with respect to 100 parts by mass of the [X] polymer. Used in an amount of 10 parts by weight. By setting the amount of the adhesion assistant in the above range, the adhesion between the formed cured film and the substrate is improved.

(Preparation of curable resin composition)
The curable resin composition of the present embodiment includes an [X] polymer, [Y] semiconductor quantum dot, [Z] polyfunctional acrylate, [V] chain transfer agent, [W] radiation sensitive polymerization initiator, and further necessary. Depending on the case, it is prepared by uniformly mixing other optional components such as a surfactant. At this time, an organic solvent can be used to prepare a curable resin composition in a dispersion state.

  That is, the curable resin composition of the present embodiment can be prepared in a state of being dissolved or dispersed in an appropriate solvent, and can be used as it is in a dispersion state. For example, in the present embodiment, the [X] component, the [Y] component, the [Z] component, the [V] component and the [W] component, and other optional components are mixed in a predetermined ratio in the organic solvent. The curable resin composition can be prepared. At this time, an organic solvent can be used individually or in mixture of 2 or more types.

  Examples of the function of the organic solvent include adjusting the viscosity and the like of the curable resin composition, and improving operability and moldability in addition to improving applicability to a substrate and the like.

  Examples of the organic solvent that can be used in the curable resin composition of the present embodiment include those that dissolve or disperse other components and that do not react with other components. Examples of such organic solvents include alcohols, ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propio. Examples thereof include nates, aromatic hydrocarbons, ketones, esters and the like.

As these organic solvents,
Examples of alcohols include benzyl alcohol and diacetone alcohol;
Examples of ethers include dialkyl ethers such as tetrahydrofuran, diisopropyl ether, di n-butyl ether, di n-pentyl ether, diisopentyl ether, and di n-hexyl ether;
Examples of diethylene glycol alkyl ethers include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether;
Examples of ethylene glycol alkyl ether acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate;
Examples of propylene glycol monoalkyl ethers include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
Examples of propylene glycol monoalkyl ether acetates include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate;
Examples of propylene glycol monoalkyl ether propionates include propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate, and the like;
Examples of aromatic hydrocarbons include toluene and xylene;
Examples of ketones include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl-2-pentanone, and the like;
Examples of esters include methyl acetate, ethyl acetate, propyl acetate, i-propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methylpropionic acid Ethyl, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, protyl 3-hydroxypropionate, 3-hydroxy Butyl propionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, ethoxy Butyl acetate, methyl propoxyacetate, ethyl propoxyacetate, propylpropoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propylbutoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2 -Propyl methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate and the like.

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

  Among these organic solvents, ethers such as diisopropyl ether such as diisopropyl ether, di n-butyl ether, di n-pentyl ether, diisopentyl ether and di n-hexyl ether are preferred, and diisopentyl ether is most preferred. preferable. By using such a solvent, when applying the curable resin composition of the present embodiment to a large glass substrate by the slit coating method, the drying process time is shortened, and at the same time, the coatability is further improved (coating unevenness is reduced). Suppression).

  In addition to the organic solvent described above, benzyl ethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1 -High-boiling solvents such as nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, carbitol acetate can be used in combination.

  The content of the organic solvent used in the curable resin composition of the present embodiment can be appropriately determined in consideration of viscosity and the like. That is, the solid content concentration of the curable resin composition of the present embodiment can be arbitrarily set according to the purpose of use and the desired film thickness, but is preferably 5% by mass to 50% by mass, more preferably It is 10 mass%-40 mass%, More preferably, it is 15 mass%-35 mass%.

  When the curable resin composition of this embodiment prepared in this way is liquid, it is used for forming the cured film of this embodiment after filtration using a Millipore filter or the like having a pore diameter of about 0.5 μm. It is preferable.

Embodiment 2. FIG.
<Curing film>
The cured film of the second embodiment of the present invention uses the curable resin composition of the first embodiment of the present invention described above, applies it on a substrate, performs patterning when necessary, and then heat cures. Formed. The cured film of the second embodiment of the present invention has a fluorescence emission (wavelength conversion) function based on [Y] semiconductor quantum dots and can be used as a wavelength conversion film or a light emitting layer. Below, the cured film and its formation method of 2nd Embodiment of this invention are demonstrated.

  In the cured film forming method of the present embodiment, it is preferable to include at least the following steps (1) to (4) in this order so that the cured film is formed on the substrate.

(1) The coating film formation process which forms the coating film of the curable resin composition of 1st Embodiment of this invention on a board | substrate.
(2) A radiation irradiation step of irradiating at least part of the coating film formed in step (1) with radiation.
(3) A development step of developing the coating film irradiated with radiation in step (2).
(4) A curing step of heating the coating film developed in step (3).

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

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

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

  FIG. 3 is a cross-sectional view of a substrate for explaining a development process in forming a cured film according to the second embodiment of the present invention.

  FIG. 4 is a cross-sectional view of a cured film and a substrate for explaining a curing process in forming a cured film according to the second embodiment of the present invention.

  Hereinafter, the above-mentioned process (1) (coating film forming process) to process (4) (curing process) will be described.

[Step (1)]
In the coating film forming process which is the process (1) of the cured film forming method of the present embodiment, the coating film 1 of the curable resin composition of the first embodiment of the present invention is applied on the substrate 2 as shown in FIG. To form.

  The substrate 2 on which the coating film 1 is formed has glass, quartz, silicon, or resin (for example, polyimide, polyethylene naphthalate, polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyester, cyclic olefin ring opening weight) For example, a substrate made of a coalescence and hydrogenated product thereof may be used. In addition, these substrates may be subjected to pretreatment such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition or the like, if desired.

  In the substrate 2, after the curable resin composition of the present embodiment is applied to one surface, prebaking is performed, components such as a solvent contained in the curable resin composition are evaporated, and the coating film 1 is formed. Is done.

  Examples of the coating method of the curable resin composition in this step include a spray method, a roll coating method, a spin coating method (sometimes called a spin coating method or a spinner method), a slit coating method (slit die coating). Method), a bar coating method, an ink jet coating method, and the like. Of these, the spin coating method or the slit coating method is preferable because a film having a uniform thickness can be formed.

  The pre-baking conditions described above vary depending on the type of each component constituting the curable resin composition, the blending ratio, etc., but it is preferably performed at a temperature of 70 ° C. to 120 ° C., and the time is heated by a hot plate, oven, or the like. Although it varies depending on the apparatus, it is about 1 minute to 15 minutes.

[Step (2)]
Next, in the radiation irradiation process which is the process (2) of the method for forming a cured film of the present embodiment, as shown in FIG. 2, at least a part of the coating film 1 formed on the substrate 2 in the process (1) is applied. Radiation 4 is irradiated. At this time, in order to irradiate only a part of the coating film 1 with the radiation 4a, for example, it is performed through the photomask 3 having a pattern corresponding to formation of a desired shape. By using this photomask 3, a part of the irradiated radiation 4 passes through the photomask, and a part of the radiation 4 a is irradiated onto the coating film 1.

  Examples of the radiation 4 used for irradiation include visible light, ultraviolet light, and far ultraviolet light. Of these, radiation having a wavelength in the range of 200 nm to 550 nm is preferable, and radiation including ultraviolet light of 365 nm is more preferable.

The dose of radiation 4 (exposure amount), the intensity at the wavelength 365nm radiation 4 as a value measured by a luminometer (OAI model 356, Optical Associates Ltd. ^Inc.), be 10J / ^{m 2} ~10000J / m 2 can be ^{preferably 100J / m 2 ~5000J / m 2} , 200J / m 2 ~3000J / m 2 is more preferable.

[Step (3)]
Next, in the development step which is step (3) of the method for forming a cured film of this embodiment, as shown in FIG. 3, the coating film 1 of FIG. 2 after irradiation is developed to remove unnecessary portions. The coating film 1a patterned into a predetermined shape is obtained.

  Examples of the developer used for development include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia, and tetramethylammonium hydroxide and tetraethylammonium hydroxide. Aqueous solutions of alkaline compounds such as quaternary ammonium salts, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0] -5-nonene Can be used. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol can be added to the aqueous solution of the alkaline compound described above. Furthermore, the surfactant can be used alone or in combination with the above-mentioned water-soluble organic solvent.

  The developing method may be any of a liquid filling method, a dipping method, a shower method, a spraying method, etc., and the developing time can be 5 seconds to 300 seconds at room temperature, preferably 10 seconds to 180 seconds at room temperature. is there. Subsequent to the development processing, for example, washing with running water is performed for 30 seconds to 90 seconds, and then a desired pattern is obtained by air drying with compressed air or compressed nitrogen.

[Step (4)]
Next, in the curing step which is step (4) of the cured film forming method of the present embodiment, the patterned coating film 1a shown in FIG. 3 is cured (post-posted) by a suitable heating device such as a hot plate or oven. Also called bake.) Thereby, as shown in FIG. 4, the cured film 5 of this embodiment formed on the board | substrate 2 is obtained. As described above, the cured film 5 is patterned so as to have a desired shape.

  In forming the cured film 5 of the present embodiment, the curable resin composition of the first embodiment of the present invention described above is used, and the heating temperature in this step is preferably 100 ° C to 250 ° C. For example, the curing time is preferably 5 to 30 minutes on a hot plate, and preferably 30 to 180 minutes in an oven.

  The cured film of this embodiment formed by the cured film forming method including the above steps (1) to (4) is configured to include [Y] semiconductor quantum dots in the resin, and [Y] semiconductor quantum. Fluorescence emission (wavelength conversion) function based on dots. Therefore, it can be used as a wavelength conversion film that emits fluorescence having a wavelength different from that of excitation light. Therefore, the wavelength conversion film of the embodiment of the present invention can be formed using the curable resin composition of the first embodiment of the present invention according to the above-described method for forming a cured film of the present embodiment. And the wavelength conversion film of this embodiment has the fluorescence light emission (wavelength conversion) function based on a [Y] 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 particular, as described later, the cured film of the second embodiment of the present invention is suitable for use as a light emitting layer of a light emitting display element that is an example of a light emitting element, and can be used for the configuration of the light emitting display element. In that case, the light emitting layer of the light emitting device of the embodiment of the present invention is similarly formed using the curable resin composition of the first embodiment of the present invention and according to the cured film forming method of the present embodiment described above. Can do. And the light emitting layer of the light emitting element of this embodiment has the fluorescence emission (wavelength conversion) function based on a [Y] semiconductor quantum dot.

  Therefore, in the cured film of this embodiment, the total light transmittance (JIS K7105) at a thickness of 0.1 mm is preferably 75% to a resin constituting the cured film so that the light use efficiency can be increased. 95%, more preferably 78% to 95%, still more preferably 80% to 95%. When the total light transmittance is within such a range, the obtained cured film can constitute a wavelength conversion film having excellent light utilization efficiency and a light emitting layer of a light emitting element.

Embodiment 3 FIG.
<Light-emitting display element and light-emitting layer thereof>
In this invention, light emitting elements, such as an illuminating device and a light emitting display element, can be provided by using as a wavelength conversion film or a light emitting layer using the cured film of 2nd Embodiment of this invention mentioned above.

  Therefore, the light emitting display element which is 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.

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

  The light emitting display element 100 according to the third embodiment of the present invention includes a wavelength conversion substrate 11 configured by providing a light emitting layer 13 (13a, 13b, 13c) and a black matrix 14 on a substrate 12, and a wavelength conversion substrate 11. And a light source substrate 18 bonded through an adhesive layer 15.

  The substrate 12 is made of glass, quartz, or a transparent resin (for example, 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 by using the cured film of the second embodiment of the present invention described above. That is, the light emitting layer 13 is formed by patterning using the curable resin composition of the first embodiment of the present invention described 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 2nd Embodiment of this invention mentioned above.
That is, the cured film of the second embodiment of the present invention is formed on the substrate 12, and these serve as the light emitting layer 13 to constitute the wavelength conversion substrate 11 of the light emitting display element 100. Therefore, the method for forming the light emitting layer 13 preferably includes the following steps (1) to (4) similar to those described above in this order.

(1) The coating film formation process which forms the coating film of the curable resin composition of 1st Embodiment of this invention on a board | substrate.
(2) A radiation irradiation step of irradiating at least part of the coating film formed in step (1) with radiation.
(3) A development step of developing the coating film irradiated with radiation in step (2).
(4) A curing step of heating the coating film developed in step (3).

  And each of (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 details are omitted, the cured film 5 patterned so as to have a desired shape shown in FIG. 4 becomes the light emitting layer 13 of the wavelength conversion substrate 11 of FIG.

  In the wavelength conversion substrate 11, each of the light emitting layers 13 uses semiconductor quantum dots contained therein, converts the wavelength of excitation light from the excitation light source 17 of the light source substrate 18, and emits fluorescence having a desired wavelength.

  And in the wavelength conversion board | substrate 11, the light emitting layer 13a, the light emitting layer 13b, and the light emitting layer 13c are respectively comprised including a different semiconductor quantum dot, and can light-emit different fluorescence.

For example, in the wavelength conversion substrate 11, the light emitting layer 13a converts excitation light into red light, the light emitting layer 13b converts excitation light into green light, and the light emitting layer 13c converts excitation light into blue light. Can be configured.
In that case, the semiconductor quantum dots to be contained 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, three kinds of curable resin compositions of the first embodiment including semiconductor quantum dots having different light emission characteristics are prepared.

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

  The thickness of the light emitting layer 13 of the wavelength conversion substrate 11 is preferably about 100 nm to 100 μm, and more preferably 1 μm to 100 μm. If the thickness is less than 100 nm, 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. Furthermore, in order to enhance absorption of excitation light and sufficiently secure the luminance of the light emitting display element, the film thickness is preferably 1 μm or more.

  A black matrix 14 is disposed between the light emitting layers 13 on the substrate 12. The black matrix 14 can be formed by using a known light-shielding material and patterning it according to a known method. Note that the black matrix 14 is not an essential component in the wavelength conversion substrate 11, and the wavelength conversion substrate 11 may be configured without the black matrix 14.

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

  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. Each of the light sources 17 emits ultraviolet light or blue light as excitation light.

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

  The light emitting display element 100 of this embodiment converts the wavelength of the excitation light from the light source 17a by the semiconductor quantum dots of the light emitting layer 13a of the wavelength conversion substrate 11 that faces the light emitting display element 100. Similarly, the wavelength of excitation light from the light source 17b is converted by the semiconductor quantum dots of the light emitting layer 13b of the opposing wavelength conversion substrate 11, and the light emission layer 13c of the wavelength conversion substrate 11 of the opposing wavelength conversion substrate 11 is converted. Wavelength conversion is performed by using semiconductor quantum dots. In this way, the excitation light from the light source 17 is converted into visible light having a desired wavelength and used for display.

  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. At this time, instead of the light emitting layer 13c, the wavelength conversion substrate 11 may use a light scattering layer configured by dispersing photoacid scattering particles in a resin. By doing so, when the excitation light is blue light, the excitation light can be used as it is without converting the wavelength.

  As described above, the wavelength conversion substrate 11 of the light-emitting display element 100 is provided with the light-emitting layer 13a, the light-emitting layer 13b, and the light-emitting layer 13c made of semiconductor quantum dots and resin, respectively, patterned on the substrate 12. Is. The light emitting layers 13a, 13b, and 13c are each formed from the curable resin composition of the first embodiment including semiconductor quantum dots.

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

  The light-emitting display element 100 includes one pixel that is a minimum unit constituting an image by three types of a sub-pixel including the light-emitting layer 13a, a sub-pixel including the light-emitting layer 13b, and a sub-pixel including the light-emitting layer 13c. Configure.

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

  In the light emitting display element 100 according to the embodiment of the present invention, a color filter can be provided between the light emitting layer 13 and the substrate 12. That is, a red color filter is provided between the light emitting layer 13a and the substrate 12, a green color filter is provided between the light emitting layer 13b and the substrate 12, and a red color filter is provided between the light emitting layer 13c and the substrate 12. Can be provided.

  The light emitting display element 100 according to the third embodiment of the present invention can increase the purity of display color by providing a color filter. Here, as a color filter, what is known for liquid crystal display elements etc. can be formed and used by a well-known method.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to these Examples at all.

<Semiconductor quantum dots>
[Y] semiconductor quantum dots used in this example are shown below.
Semiconductor quantum dot A: InP / ZnS core-shell quantum dot semiconductor quantum dot B: InCuS ₂ / ZnS core-shell quantum dot semiconductor quantum dot C: Si quantum dot

The semiconductor quantum dots A: InP / ZnS core-shell quantum dots, semiconductor quantum dots B: InCuS ₂ / ZnS core-shell quantum dots, and semiconductor quantum dots C: Si quantum dots used in the following examples are as follows: It can be synthesized by a generally known method.

For example, regarding the semiconductor quantum dot A: InP / ZnS core-shell type quantum dot, the technical literature “Journal of American Chemical Society. 2007, 129, 15432-15433” and the semiconductor quantum dot B: InCuS ₂ / ZnS core-shell type quantum dot In the technical document “Journal of American Chemical Society. 2009, 131, 5691-5697” and the technical document “Chemistry of Materials. 2009, 21, 2422-2429”, regarding the semiconductor quantum dot C: American Chemical Society. 2010, 132, 248-253 ”. It can be synthesized with reference to the method.

<Preparation of curable resin composition>
Synthesis example 1
[Synthesis of Copolymer (α)]
The synthesis of the copolymer (α), which is the [X] polymer that is a component of the curable resin composition, was performed as follows.
A flask equipped with a condenser and a stirrer was charged with 4 parts by mass of 2,2′-azobisisobutyronitrile and 190 parts by mass of propylene glycol monomethyl ether acetate, and subsequently 55 parts by mass of methacrylic acid and 45 parts by mass of benzyl methacrylate. In addition, 2 parts by mass of α-methylstyrene dimer as a molecular weight regulator was added, and while gently stirring, the temperature of the solution was raised to 80 ° C., this temperature was maintained for 4 hours, and then raised to 100 ° C. A solution containing a copolymer was obtained by polymerization while maintaining the temperature for 1 hour. Next, 1.1 parts by mass of tetrabutylammonium bromide and 0.05 parts by mass of 4-methoxyphenol as a polymerization inhibitor were added to the solution containing this copolymer, and the mixture was stirred at 90 ° C. for 30 minutes in an air atmosphere. A copolymer (α) was obtained by adding 74 parts by mass of glycidyl acid and reacting at 90 ° C. for 10 hours (solid content concentration = 35.0%). The Mw of the copolymer (α) was 9000.
In this ^case, 1 H-NMR, was determined from FT-IR, in the copolymer (alpha), the content of the above (X1) structural units was 37.5mol%.

Synthesis example 2
[Synthesis of Copolymer (β)]
[X] The copolymer (β) as a polymer was synthesized according to the following.
A flask equipped with a condenser and a stirrer was charged with 4 parts by weight of 2,2′-azobisisobutyronitrile and 190 parts by weight of propylene glycol monomethyl ether acetate, followed by 85 parts by weight of methacrylic acid and 15 parts by weight of benzyl methacrylate. In addition, 2 parts by mass of α-methylstyrene dimer as a molecular weight regulator was added, and while gently stirring, the temperature of the solution was raised to 80 ° C., this temperature was maintained for 4 hours, and then raised to 100 ° C. A solution containing a copolymer was obtained by polymerization while maintaining the temperature for 1 hour. Next, 1.1 parts by mass of tetrabutylammonium bromide and 0.05 parts by mass of 4-methoxyphenol as a polymerization inhibitor were added to the solution containing this copolymer, and the mixture was stirred at 90 ° C. for 30 minutes in an air atmosphere. A copolymer (β) was obtained by adding 74 parts by mass of glycidyl acid and reacting at 90 ° C. for 10 hours (solid content concentration = 35.5%). The Mw of the copolymer (β) was 10,000.
At this time, the content of the (X1) structural unit in the copolymer (β) determined from ¹ H-NMR and FT-IR was 8.5 mol%.

Example 1
[Preparation of Curable Resin Composition (δ-I)]

  [X] MAX as a polyfunctional acrylate as the [Z] component in a solution containing the copolymer (α) synthesized in Synthesis Example 1 as a polymer (amount corresponding to 100 parts by mass (solid content) of the copolymer). -3510 (manufactured by Nippon Kayaku Co., Ltd.), pentaerythritol tetrakis (3-mercaptobutyrate) which is a compound having a mercapto group as a chain transfer agent which is the [V] component (manufactured by Showa Denko KK) Name: 10 parts by mass of Karenz MT-PE1), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (Ciba 3 parts by mass of Irgacure (registered trademark) 907) manufactured by Specialty Chemicals, SH8400 FLUID (Toray Dow Corning Cone Co., Ltd.) 0.3 parts by weight was added and mixed and dissolved, and then 10 parts by weight of semiconductor quantum dots A as the [Y] component were mixed to prepare a curable resin composition (δ-I). did.

Example 2
[Preparation of Curable Resin Composition (δ-II)]
In this Example 2, the curable resin composition (δ-II) was the same as Example 1 except that the semiconductor quantum dot B was used instead of the semiconductor quantum dot A as the semiconductor quantum dot of the [Y] component. Was prepared.

Example 3
[Preparation of Curable Resin Composition (δ-III)]
In the present Example 3, the curable resin composition (δ-III) is the same as the Example 1 except that the semiconductor quantum dot C is used instead of the semiconductor quantum dot A as the semiconductor quantum dot of the [Y] component. Was prepared.

Example 4
[Preparation of Curable Resin Composition (δ-IV)]
In this Example 4, a solution containing the copolymer (β) synthesized in Synthesis Example 2 (amount corresponding to 100 parts by mass (solid content) of the copolymer) was used as the [X] polymer. In the same manner as in Example 1, a curable resin composition (δ-IV) was prepared.

Example 5
[Preparation of Curable Resin Composition (δ-V)]
In Example 5, 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2 which is a compound having a mercapto group as the chain transfer agent which is the [V] component , 4,6- (1H, 3H, 5H) -trione (trade name: Karenz MT-NR1 manufactured by Showa Denko KK) was used in the same manner as in Example 1 except that 15 parts by mass was used. (Δ-V) was prepared.

Example 6
[Preparation of Curable Resin Composition (δ-VI)]
In this Example 6, 1,4-bis (3-mercaptobutyryloxy) butane (made by Showa Denko KK), which is a compound having a mercapto group, as the chain transfer agent which is the [V] component, trade name: Karenz MT A curable resin composition (δ-VI) was prepared in the same manner as in Example 1 except that 20 parts by mass of -BD1) was used.

Comparative Example 1
[Preparation of Curable Resin Composition (δ-VII)]
In Comparative Example 1, a curable resin composition (δ-VII) as a first comparative example was prepared in the same manner as in Example 1 except that the chain transfer agent of the [V] component was not used.

<Evaluation of cured film>
Using the curable resin composition prepared in Example 1 to Example 6 and the curable resin composition prepared in Comparative Example 1, a cured film was formed as follows, and the characteristics were evaluated.

Example 7
[Formation of cured film using curable resin composition (δ-I)]
A curable resin composition (δ-I) prepared in Example 1 was applied on an alkali-free glass substrate by a spin coating method, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film. .
Next, radiation was applied to the obtained coating film through a photomask having a predetermined pattern with an exposure amount of 700 J / m ² using a high-pressure mercury lamp. Next, development was performed at 25 ° C. for 60 seconds with a 0.4 mass% tetramethylammonium hydroxide aqueous solution.
Next, a cured film patterned into a predetermined shape was formed by post-baking in an oven at a curing temperature of 180 ° C. and a curing time of 30 minutes.

Next, the edge part of the patterned cured film was observed with an optical microscope, and it was judged that the patterning property was good when there was no development residue and the linear part of the pattern was linearly formed.
As a result, the patterning property of the cured film formed by patterning using the curable resin composition (δ-I) was good.

Example 8
[Formation of cured film using curable resin composition (δ-II)]
The curable resin composition (δ-II) prepared in Example 2 was applied on an alkali-free glass substrate with a spinner, and then prebaked on a 90 ° C. hot plate for 2 minutes to form a coating film.
Next, the obtained coating film was irradiated with radiation at an exposure amount of 1000 J / m ² through a photomask having a predetermined pattern using a high-pressure mercury lamp, and a 0.4 mass% tetramethylammonium hydroxide aqueous solution Development was performed at 25 ° C. for 150 seconds.
Next, a cured film patterned into a predetermined shape was formed by post-baking in an oven at a curing temperature of 180 ° C. and a curing time of 30 minutes.

Next, the edge part of the patterned cured film was observed with an optical microscope, and it was judged that the patterning property was good when there was no development residue and the linear part of the pattern was linearly formed.
As a result, the patterning property of the cured film formed by patterning using the curable resin composition (δ-II) was good.

Example 9
[Formation of cured film using curable resin composition (δ-III)]
The curable resin composition (δ-III) prepared in Example 3 was applied on an alkali-free glass substrate with a spinner, and then prebaked on a hot plate at 100 ° C. for 2 minutes to form a coating film.
Next, the obtained coating film was irradiated with radiation at an exposure amount of 800 J / m ² using a high-pressure mercury lamp through a photomask having a predetermined pattern, and a 0.4% by mass aqueous tetramethylammonium hydroxide solution was obtained. Development was performed at 25 ° C. for 80 seconds.
Next, a cured film patterned into a predetermined shape was formed by post-baking in an oven at a curing temperature of 180 ° C. and a curing time of 30 minutes.

Next, the edge part of the patterned cured film was observed with an optical microscope, and it was judged that the patterning property was good when there was no development residue and the linear part of the pattern was linearly formed.
As a result, the patternability of the cured film formed by patterning using the curable resin composition (δ-III) was good.

Example 10
[Formation of cured film using curable resin composition (δ-IV)]
A curable resin composition (δ-IV) prepared in Example 3 was applied onto an alkali-free glass substrate with a spinner, and then prebaked on a hot plate at 100 ° C. for 2 minutes to form a coating film.
Next, the obtained coating film was irradiated with radiation at an exposure amount of 800 J / m ² using a high-pressure mercury lamp through a photomask having a predetermined pattern, and a 0.4% by mass aqueous tetramethylammonium hydroxide solution was obtained. Development was performed at 25 ° C. for 80 seconds.
Next, a cured film patterned into a predetermined shape was formed by post-baking in an oven at a curing temperature of 180 ° C. and a curing time of 30 minutes.

Next, the edge part of the patterned cured film was observed with an optical microscope, and it was judged that the patterning property was good when there was no development residue and the linear part of the pattern was linearly formed.
As a result, the patterning property of the cured film formed by patterning using the curable resin composition (δ-IV) was good.

Example 11
[Formation of cured film using curable resin composition (δ-V)]
A curable resin composition (δ-V) prepared in Example 3 was applied on an alkali-free glass substrate with a spinner, and then prebaked on a hot plate at 100 ° C. for 2 minutes to form a coating film.
Next, the obtained coating film was irradiated with radiation at an exposure amount of 800 J / m ² using a high-pressure mercury lamp through a photomask having a predetermined pattern, and a 0.4% by mass aqueous tetramethylammonium hydroxide solution was obtained. Development was performed at 25 ° C. for 80 seconds.
Next, a cured film patterned into a predetermined shape was formed by post-baking in an oven at a curing temperature of 180 ° C. and a curing time of 30 minutes.

Next, the edge part of the patterned cured film was observed with an optical microscope, and it was judged that the patterning property was good when there was no development residue and the linear part of the pattern was linearly formed.
As a result, the patterning property of the cured film formed by patterning using the curable resin composition (δ-V) was good.

Example 12
[Formation of cured film using curable resin composition (δ-VI)]
The curable resin composition (δ-VI) prepared in Example 3 was applied onto an alkali-free glass substrate with a spinner, and then prebaked on a hot plate at 100 ° C. for 2 minutes to form a coating film.
Next, the obtained coating film was irradiated with radiation at an exposure amount of 800 J / m ² using a high-pressure mercury lamp through a photomask having a predetermined pattern, and a 0.4% by mass aqueous tetramethylammonium hydroxide solution was obtained. Development was performed at 25 ° C. for 80 seconds.
Next, a cured film patterned into a predetermined shape was formed by post-baking in an oven at a curing temperature of 180 ° C. and a curing time of 30 minutes.

Next, the edge part of the patterned cured film was observed with an optical microscope, and it was judged that the patterning property was good when there was no development residue and the linear part of the pattern was linearly formed.
As a result, the patterning property of the cured film formed by patterning using the curable resin composition (δ-VI) was good.

Comparative Example 2
[Formation of cured film using curable resin composition (δ-VII)]
A curable resin composition (δ-VII) prepared in Comparative Example 1 was applied on an alkali-free glass substrate with a spinner, and then prebaked on a hot plate at 100 ° C. for 2 minutes to form a coating film.
Next, the obtained coating film was irradiated with radiation at an exposure amount of 800 J / m ² using a high-pressure mercury lamp through a photomask having a predetermined pattern, and a 0.4% by mass aqueous tetramethylammonium hydroxide solution was obtained. Development was performed at 25 ° C. for 80 seconds.
Next, a cured film patterned into a predetermined shape was formed by post-baking in an oven at a curing temperature of 180 ° C. and a curing time of 30 minutes.

Next, the edge part of the patterned cured film was observed with an optical microscope, and it was judged that the patterning property was good when there was no development residue and the linear part of the pattern was linearly formed.
As a result, the patterning property of the cured film formed by patterning using the curable resin composition (δ-VII) was good.

Example 13
[Evaluation of curing shrinkage]
The cured film obtained by the forming method of Example 7 was further subjected to an exposure treatment of 1 J / cm ² , and the film thickness before and after this exposure was measured with a stylus type film thickness measuring machine (Alphastep IQ, KLA Tencor). And the remaining film rate (film thickness after a process / film thickness before a process x100) was computed, and this remaining film rate was made into hardening shrinkage. The residual film ratio was 99%, and the curing shrinkage was judged to be good.

Similarly, the cured film obtained by the formation method of Example 8 was further subjected to an exposure treatment of 1 J / cm ² , and the film thickness before and after this exposure was measured with a stylus type film thickness measuring machine (Alphastep IQ, KLA Tencor). did. And the remaining film rate (film thickness after a process / film thickness before a process x100) was computed, and this remaining film rate was made into hardening shrinkage. The residual film ratio was 99%, and the curing shrinkage was judged to be good.

Similarly, the cured film obtained by the formation method of Example 9 was further subjected to an exposure treatment of 1 J / cm ² , and the film thickness before and after this exposure was measured with a stylus type film thickness measuring machine (Alphastep IQ, KLA Tencor). did. And the remaining film rate (film thickness after a process / film thickness before a process x100) was computed, and this remaining film rate was made into hardening shrinkage. The residual film ratio was 99%, and the curing shrinkage was judged to be good.

Similarly, the cured film by the forming method of Example 10 was further subjected to an exposure treatment of 1 J / cm ² , and the film thickness before and after this exposure was measured with a stylus type film thickness measuring machine (Alphastep IQ, KLA Tencor). did. And the remaining film rate (film thickness after a process / film thickness before a process x100) was computed, and this remaining film rate was made into hardening shrinkage. The residual film ratio was 99%, and the curing shrinkage was judged to be good.

Similarly, the cured film obtained by the formation method of Example 11 was further subjected to an exposure process of 1 J / cm ² , and the film thickness before and after this exposure was measured with a stylus type film thickness measuring machine (Alphastep IQ, KLA Tencor). did. And the remaining film rate (film thickness after a process / film thickness before a process x100) was computed, and this remaining film rate was made into hardening shrinkage. The residual film ratio was 99%, and the curing shrinkage was judged to be good.

Similarly, the cured film obtained by the formation method of Example 12 was further subjected to an exposure treatment of 1 J / cm ² , and the film thickness before and after this exposure was measured with a stylus type film thickness measuring device (Alphastep IQ, KLA Tencor). did. And the remaining film rate (film thickness after a process / film thickness before a process x100) was computed, and this remaining film rate was made into hardening shrinkage. The residual film ratio was 99%, and the curing shrinkage was judged to be good.

Similarly, the cured film formed by the formation method of Comparative Example 2 is further subjected to an exposure process of 1 J / cm ² , and the film thickness before and after this exposure is measured with a stylus type film thickness measuring machine (Alphastep IQ, KLA Tencor). did. And the remaining film rate (film thickness after a process / film thickness before a process x100) was computed, and this remaining film rate was made into hardening shrinkage. The residual film ratio was 99%, and the curing shrinkage was judged to be good.

Example 14
[Evaluation of light resistance]
About the cured film by the formation method of Example 7, further, UV irradiation apparatus (UVX-02516S1JS01, Ushio Inc.) was used to irradiate 800,000 J / m ² of ultraviolet light at an illuminance of 130 mW, and the film reduction after irradiation I investigated. The amount of film loss was 2% or less, and light resistance was judged to be good.

Similarly, the cured film obtained by the formation method of Example 8 was further irradiated with UV light of 800000 J / m ² at an illuminance of 130 mW using a UV irradiation apparatus (UVX-02516S1JS01, Ushio Inc.). The amount of film loss was examined. The amount of film loss was 2% or less, and light resistance was judged to be good.

Similarly, the cured film formed by the formation method of Example 9 was further irradiated with UV light of 800000 J / m ² at an illuminance of 130 mW using a UV irradiation apparatus (UVX-02516S1JS01, Ushio Inc.). The amount of film loss was examined. The amount of film loss was 2% or less, and light resistance was judged to be good.

Similarly, the cured film obtained by the formation method of Example 10 was further irradiated with 80000 J / m ² of ultraviolet light at an illuminance of 130 mW using a UV irradiation apparatus (UVX-02516S1JS01, Ushio Inc.). The amount of film loss was examined. The amount of film loss was 2% or less, and light resistance was judged to be good.

Similarly, the cured film obtained by the formation method of Example 11 was further irradiated with 80000 J / m ² of ultraviolet light at an illuminance of 130 mW using a UV irradiation apparatus (UVX-02516S1JS01, Ushio Inc.). The amount of film loss was examined. The amount of film loss was 2% or less, and light resistance was judged to be good.

Similarly, the cured film obtained by the formation method of Example 12 was further irradiated with UV light of 800000 J / m ² at an illuminance of 130 mW using a UV irradiation apparatus (UVX-02516S1JS01, Ushio Inc.). The amount of film loss was examined. The amount of film loss was 2% or less, and light resistance was judged to be good.

Similarly, the cured film formed by the formation method of Comparative Example 2 was further irradiated with 80000 J / m ² of ultraviolet light at an illuminance of 130 mW using a UV irradiation apparatus (UVX-02516S1JS01, Ushio Inc.). The amount of film loss was examined. The amount of film loss was 2% or less, and light resistance was judged to be good.

Example 15
[Evaluation of fluorescence characteristics]
For the cured film obtained by the formation method of Example 7, the fluorescence quantum yield at 25 ° C. was further examined using an absolute PL quantum yield measuring apparatus (C11347-01, Hamamatsu Photonics). The fluorescence quantum yield was 80%, and the fluorescence characteristics were judged to be good.

  Similarly, the fluorescence quantum yield at 25 ° C. of the cured film obtained by the formation method of Example 8 was further examined using an absolute PL quantum yield measuring apparatus (C11347-01, Hamamatsu Photonics). The fluorescence quantum yield was 71%, and the fluorescence characteristics were judged to be good.

  Similarly, the fluorescence quantum yield at 25 ° C. of the cured film obtained by the formation method of Example 9 was further examined using an absolute PL quantum yield measuring apparatus (C11347-01, Hamamatsu Photonics). The fluorescence quantum yield was 63%, and the fluorescence characteristics were judged to be good.

  Similarly, the fluorescence quantum yield at 25 ° C. of the cured film obtained by the formation method of Example 10 was further examined using an absolute PL quantum yield measuring apparatus (C11347-01, Hamamatsu Photonics). The fluorescence quantum yield was 79%, and the fluorescence characteristics were judged to be good.

  Similarly, the fluorescence quantum yield at 25 ° C. of the cured film obtained by the formation method of Example 11 was further examined using an absolute PL quantum yield measuring apparatus (C11347-01, Hamamatsu Photonics). The fluorescence quantum yield was 80%, and the fluorescence characteristics were judged to be good.

  Similarly, the fluorescence quantum yield at 25 ° C. of the cured film obtained by the formation method of Example 12 was further examined using an absolute PL quantum yield measuring apparatus (C11347-01, Hamamatsu Photonics). The fluorescence quantum yield was 80%, and the fluorescence characteristics were judged to be good.

  Similarly, the fluorescence quantum yield at 25 ° C. of the cured film obtained by the formation method of Comparative Example 2 was further examined using an absolute PL quantum yield measuring apparatus (C11347-01, Hamamatsu Photonics). The fluorescence quantum yield was 15%, which resulted in a significant decrease in fluorescence characteristics.

  The cured film formed by using the curable resin composition of the present invention is excellent in reliability such as light resistance and is easily patterned, and the display element and the wavelength conversion film are used as a wavelength conversion layer or a wavelength conversion film. In addition to the electronic devices that have been used, the present invention can also be used in the fields of LEDs, lighting devices using the LEDs, and solar cells.

1, 1a Coating 2, 12, 16 Substrate 3 Photomask 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 (10)

[X] alkali-soluble resin,
[Y] semiconductor quantum dots,
[Z] polyfunctional acrylate,
A curable resin composition comprising [V] a chain transfer agent and [W] a radiation-sensitive polymerization initiator.   The curable resin according to claim 1, wherein the [X] alkali-soluble resin is a polymer containing (X1) a structural unit having an aromatic ring and (X2) a structural unit having a (meth) acryloyloxy group. Resin composition.   [X] Content of the structural unit which has (X1) aromatic ring in alkali-soluble resin is 20 mol%-90 mol% of the whole [X] polymer, The curable resin of Claim 2 characterized by the above-mentioned. Composition.   [Y] The curable resin composition according to any one of claims 1 to 3, wherein the semiconductor quantum dot is made of a compound containing In as a constituent component. [Y] At least one 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. It is a seed | species, The curable resin composition of any one of Claims 1-4 characterized by the above-mentioned.   The curable resin composition according to any one of claims 1 to 5, wherein the chain transfer agent includes a compound having a mercapto group.   A cured film formed using the curable resin composition according to any one of claims 1 to 6. A light emitting element comprising a light emitting layer that emits fluorescence by excitation light formed using the curable resin composition according to claim 1.   A wavelength conversion film formed using the curable resin composition according to any one of claims 1 to 6. A method of forming a light emitting layer that emits fluorescence by excitation light of a light emitting element,
(1) The process of forming the coating film of the curable resin composition of any one of Claims 1-6 on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) A step of developing the coating film irradiated with radiation in the step (2), and (4) a step of heating the coating film developed in the step (3). .

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