JP6299546B2 - Curable resin composition, cured film, wavelength conversion film, light emitting element, and method for forming light emitting layer - Google Patents

Description

  The present invention relates to a curable resin composition, a cured film, a wavelength conversion film, a light emitting element, 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 (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. Accordingly, there is a demand for the formation of quantum dots made of safer materials.

  In addition, when applying quantum dots to a solar cell panel, a display of a display element, or the like, formation of a film or layer composed of particle-shaped quantum dots 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 quantum dots in the form of particles, for example, as shown in Examples of Patent Document 1 and Patent Document 2, a layer made of quantum dots is directly formed on an appropriate substrate. How to do is known. However, in such a formation method, the stability of the obtained light emitting layer is poor. In particular, there is a concern about the binding property between the layer made of quantum dots and the substrate.

  Therefore, a method for forming a layer or a film by mixing or embedding a particle-form quantum dot in a resin material has been proposed. However, a method for forming a layer or a film together with a resin while realizing high dispersibility using quantum dots and maintaining fluorescence characteristics as quantum dots has not been sufficiently studied.

  Therefore, there is a need for a technique that uses quantum dots together with a resin material to form a quantum dot layer or film without realizing high dispersibility and reducing the fluorescence emission characteristics of the quantum dots. And the technique which forms a highly reliable light emitting layer or wavelength conversion film excellent in light resistance etc. including a quantum dot is calculated | required. In particular, a resin material that is used together with quantum dots and is suitable for forming a light-emitting layer or a wavelength conversion film composed of quantum dots and a resin is required.

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

  In addition, it is preferable that the light emitting layer and the wavelength conversion film made of the quantum dots and the resin material can be easily formed and have high productivity. Therefore, it is preferable that a simple forming method such as coating can be used for forming a light emitting layer or a wavelength conversion film made of the quantum dots and the resin material. 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 quantum dot and a resin component, for example.

  Therefore, there is a demand for a resin composition that is prepared containing quantum dots and a resin component and that can form a light emitting layer and a wavelength conversion film by using a method such as coating.

  Furthermore, it is preferable that the resin composition has an excellent patterning property. That is, the resin composition forming the light emitting layer and the wavelength conversion film can be patterned, and for example, it can be preferably used for the configuration of a light emitting element such as a light emitting display element. In that case, the formation of the patterned light-emitting layer or wavelength conversion film can be performed easily, for example, by using a photolithography method or the like.

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

  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 can easily form a highly reliable cured film containing quantum dots and exhibiting excellent fluorescence characteristics.

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

  Another object of the present invention is to provide a highly reliable wavelength conversion film which is formed using a curable resin composition containing quantum dots and has excellent fluorescence characteristics.

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

  Furthermore, the objective of this invention is providing the formation method of the light emitting layer using the curable resin composition containing a 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:
[A] It relates to a curable resin composition containing a structural moiety represented by the following formula (1) and a polymer having a structural moiety represented by the following formula (2), and [B] quantum dots.

(In Formula (1), X ¹ represents a hydrogen atom or a monovalent linear or branched saturated hydrocarbon group having 1 to 3 carbon atoms. X ² represents 1 having 3 to 30 carbon atoms. One or more of a valent linear, branched or cyclic saturated or unsaturated hydrocarbon group or a monovalent linear, branched or cyclic saturated or unsaturated hydrocarbon group having 3 to 30 carbon atoms In which a hydrogen atom is substituted with a hydroxy group, a halogen atom, a nitro group, a carboxyl group, an alkyl group which may have a substituent, an aralkyl group, or an alkoxy group.
In formula (2), Y ¹ represents a hydrogen atom or a methyl group. Y ² represents a C 1-12 divalent linear, branched or cyclic saturated or unsaturated hydrocarbon group or a C 1-12 divalent linear, branched or cyclic saturated or A group in which one or more hydrogen atoms of an unsaturated hydrocarbon group are substituted with a hydroxy group, a halogen atom, a nitro group, a carboxyl group, an optionally substituted alkyl group, an aralkyl group, or an alkoxy group . Y ³ represents a divalent organic group. Y ⁴ represents a hydrogen atom, a monovalent linear, branched or cyclic hydrocarbon group having 1 to 12 carbon atoms, or a divalent linear, branched or cyclic group having 1 to 12 carbon atoms. One or more hydrogen atoms of the saturated or unsaturated hydrocarbon group of is substituted with a hydroxy group, a halogen atom, a nitro group, a carboxyl group, an optionally substituted alkyl group, an aralkyl group, or an alkoxy group Indicates a group. n represents 0 or 1. )

  In the first aspect of the present invention, the [B] quantum dot is at least selected from the group consisting of a group 2 element, a group 11 element, a group 12 element, a group 13 element, a group 14 element, a group 15 element and a group 16 element. It is preferably made of a compound containing two kinds of elements.

  1st aspect of this invention WHEREIN: It is preferable that a [B] quantum dot consists of a compound which contains In as a structural component.

In the first aspect of the present invention, the [B] 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 an Si compound. It is preferably at least one selected from the group consisting of:

  In the first embodiment of the present invention, it is preferable that a polymerization initiator [C] is further contained.

  1st aspect of this invention WHEREIN: Furthermore, it is preferable that a [C] polymerization initiator is contained and a [C] polymerization initiator is a polymerization initiator which does not have a nitrogen atom in a molecule | numerator.

  In the first aspect of the present invention, it is preferable that a [D] polymerizable unsaturated compound is further contained.

  In the first aspect of the present invention, it is preferable to further contain [E] an antioxidant.

  1st aspect of this invention WHEREIN: Furthermore, it is preferable that [E] antioxidant is contained and [E] antioxidant is a phosphite type | system | group antioxidant.

  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 wavelength conversion film formed using the curable resin composition of the first aspect of the present invention.

  A 4th aspect of this invention is related with the light emitting element characterized by having the light emitting layer formed using the curable resin composition of the 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 step (2), and (4) a step of exposing the coating film developed in step (3). About.

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

  Moreover, according to the 2nd aspect of this invention, it forms using the curable resin composition containing a quantum dot, and the highly reliable cured film excellent in the fluorescence characteristic is provided.

  Moreover, according to the 3rd aspect of this invention, the highly reliable wavelength conversion film which was formed using the curable resin composition containing a quantum dot and was excellent in the fluorescence characteristic is provided.

  Moreover, according to the 4th aspect of this invention, the light emitting element which has a light emitting layer formed using the curable resin composition containing a quantum dot is provided.

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

It is sectional drawing of the board | substrate explaining an example of the coating-film formation process in formation of the cured film of 2nd Embodiment of this invention. It is sectional drawing which illustrates typically an example of 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 an example of 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 an example of the hardening process in formation of the cured film of 2nd Embodiment of this invention. It is sectional drawing which shows typically an example of the light emission display element which is a light emitting element of 4th Embodiment of this invention.

  The curable resin composition according to the first embodiment of the present invention includes [A] a polymer having a structural moiety represented by the following formula (1) and a structural moiety represented by the following formula (2) (hereinafter referred to as [A] And a curable resin composition containing [B] quantum dots (hereinafter also simply referred to as [B] component).

(In Formula (1), X ¹ represents a hydrogen atom or a monovalent linear or branched saturated hydrocarbon group having 1 to 3 carbon atoms. X ² represents 1 having 3 to 30 carbon atoms. One or more of a valent linear, branched or cyclic saturated or unsaturated hydrocarbon group or a monovalent linear, branched or cyclic saturated or unsaturated hydrocarbon group having 3 to 30 carbon atoms In which a hydrogen atom is substituted with a hydroxy group, a halogen atom, a nitro group, a carboxyl group, an alkyl group which may have a substituent, an aralkyl group, or an alkoxy group.
In formula (2), Y ¹ represents a hydrogen atom or a methyl group. Y ² represents a C 1-12 divalent linear, branched or cyclic saturated or unsaturated hydrocarbon group or a C 1-12 divalent linear, branched or cyclic saturated or A group in which one or more hydrogen atoms of an unsaturated hydrocarbon group are substituted with a hydroxy group, a halogen atom, a nitro group, a carboxyl group, an optionally substituted alkyl group, an aralkyl group, or an alkoxy group . Y ³ represents a divalent organic group. Y ⁴ represents a hydrogen atom, a monovalent linear, branched or cyclic hydrocarbon group having 1 to 12 carbon atoms, or a divalent linear, branched or cyclic group having 1 to 12 carbon atoms. One or more hydrogen atoms of the saturated or unsaturated hydrocarbon group of is substituted with a hydroxy group, a halogen atom, a nitro group, a carboxyl group, an optionally substituted alkyl group, an aralkyl group, or an alkoxy group Indicates a group. n represents 0 or 1. )

  The curable resin composition of 1st Embodiment of this invention contains a [A] polymer, and turns into a resin composition suitable for formation of the simple film | membrane and layer by application | coating etc.

  And the curable resin composition of 1st Embodiment of this invention can implement | achieve the favorable dispersion state of a [B] quantum dot by containing the quantum dot of a [B] component with a [A] component. it can.

  When quantum dots are used together with a resin component, a solvent, or the like to form a composition, they tend to aggregate in the composition and it is difficult to realize a good dispersion state. In a quantum dot, aggregation will impair its fluorescent properties. Therefore, in the curable resin composition of 1st Embodiment of this invention, the [A] component which is a resin component is selected and contained so that a [B] quantum dot may show a favorable dispersion state.

  As a result, the curable resin composition of 1st Embodiment of this invention can form the resin composition in which the favorable dispersion state of [B] quantum dot was implement | achieved. And the curable resin composition of 1st Embodiment of this invention can form the layer and film | membrane in which the [B] quantum dot was disperse | distributed using simple formation methods, such as application | coating.

  Moreover, the curable resin composition of 1st Embodiment of this invention can have radiation sensitivity. Therefore, the curable resin composition of the first embodiment of the present invention preferably contains [C] polymerizable initiator (hereinafter also simply referred to as [C] component), and [D] polymerizable. It is preferable to contain an unsaturated compound (hereinafter also simply referred to as [E] component). And the curable resin composition of 1st Embodiment of this invention can be patterned using the photolithographic method etc. based on the 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 second embodiment of the present invention. The cured film of 2nd Embodiment of this invention is comprised by including [B] quantum dot in resin.

  And the cured film of 2nd Embodiment of this invention can have the fluorescence emission (wavelength conversion) function based on [B] quantum dot. Therefore, it can be used as a wavelength conversion film or a light emitting layer that emits fluorescence having a wavelength different from that of excitation light.

  In particular, the cured film of the second embodiment of the present invention is suitable for use as a light emitting layer in addition to the formation of the wavelength conversion film of the third embodiment of the present invention. It can be used for the structure of a light emitting element.

  Hereinafter, the curable resin composition of the first embodiment of the present invention, the cured film of the second embodiment of the present invention, the wavelength conversion film of the third embodiment of the present invention, the light emitting device of the fourth embodiment of the present invention, And the formation method of the light emitting layer which is 5th Embodiment of this invention is demonstrated.

Embodiment 1 FIG.
<Curable resin composition>
As described above, the curable resin composition of the first embodiment of the present invention contains the [A] component and the [B] quantum dot as essential components.

  The curable resin composition of the first embodiment of the present invention includes a [A] component and [B] quantum dots, and [B] forms a resin composition in which a good dispersion state of the quantum dots is realized. Can do.

  The curable resin composition according to the first embodiment of the present invention contains a [B] quantum dot-containing excellent fluorescence emission (wavelength conversion) function (hereinafter simply referred to as fluorescence) by utilizing a method such as coating. Alternatively, a cured film according to the second embodiment of the present invention having a fluorescent property or the like can be formed.

  Moreover, the curable resin composition of 1st Embodiment of this invention can have radiation sensitivity. Therefore, as described above, the curable resin composition of the first embodiment of the present invention preferably further contains [C] a polymerizable initiator, and further contains [D] a polymerizable unsaturated compound. It is preferable to contain.

  Moreover, the curable resin composition of 1st Embodiment of this invention can contain [E] antioxidant with [A] component, [B] quantum dot, etc., and was equipped with the stable fluorescence characteristic. The cured film of 2nd Embodiment of this invention can be formed.

  And the curable resin composition of 1st Embodiment of this invention can contain the other arbitrary component mentioned above, unless the effect of this invention is impaired.

  Below, each content component of the curable resin composition of 1st Embodiment of this invention is demonstrated in detail.

[[A] polymer]
The curable resin composition of the first embodiment of the present invention is represented by [A] a structural part represented by the following formula (1) (hereinafter also simply referred to as the structural part (1)) and the following formula (2). A polymer having a structural part (hereinafter also simply referred to as a structural part (2)).

(In Formula (1), X ¹ represents a hydrogen atom or a monovalent linear or branched saturated hydrocarbon group having 1 to 3 carbon atoms. X ² represents 1 having 3 to 30 carbon atoms. One or more of a valent linear, branched or cyclic saturated or unsaturated hydrocarbon group or a monovalent linear, branched or cyclic saturated or unsaturated hydrocarbon group having 3 to 30 carbon atoms In which a hydrogen atom is substituted with a hydroxy group, a halogen atom, a nitro group, a carboxyl group, an alkyl group which may have a substituent, an aralkyl group, or an alkoxy group.
In formula (2), Y ¹ represents a hydrogen atom or a methyl group. Y ² represents a C 1-12 divalent linear, branched or cyclic saturated or unsaturated hydrocarbon group or a C 1-12 divalent linear, branched or cyclic saturated or A group in which one or more hydrogen atoms of an unsaturated hydrocarbon group are substituted with a hydroxy group, a halogen atom, a nitro group, a carboxyl group, an optionally substituted alkyl group, an aralkyl group, or an alkoxy group . Y ³ represents a divalent organic group. Y ⁴ represents a hydrogen atom, a monovalent linear, branched or cyclic hydrocarbon group having 1 to 12 carbon atoms, or a divalent linear, branched or cyclic group having 1 to 12 carbon atoms. One or more hydrogen atoms of the saturated or unsaturated hydrocarbon group of is substituted with a hydroxy group, a halogen atom, a nitro group, a carboxyl group, an optionally substituted alkyl group, an aralkyl group, or an alkoxy group Indicates a group. n represents 0 or 1. )

Examples of the monovalent linear or branched saturated hydrocarbon group having 1 to 3 carbon atoms in X ¹ of the above formula (1) include, for example, a methyl group, an ethyl group, a 1-propyl group, and a 2-propyl group. Etc. And, preferred X ¹ in the formula (1), a hydrogen atom, methyl group.

Examples of the monovalent linear or branched saturated or unsaturated hydrocarbon group having 3 to 30 carbon atoms in X ² of the formula (1) include, for example, an n-propyl group, an i-propyl group, an n- Butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, Tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, eicosyl group, heicosyl group, heicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group , Octacosyl group, nonacosyl group, triacontyl group, etc. And monovalent hydrocarbon groups derived from linear or branched alkyl groups.

In X ² of the above formula (1), one or more hydrogen atoms of a monovalent linear or branched saturated or unsaturated hydrocarbon group having 3 to 30 carbon atoms are a hydroxy group, a halogen atom, a nitro group, Examples of the group substituted with a carboxyl group, an alkyl group that may have a substituent, an aralkyl group, or an alkoxy group include the following groups. That is, as such a group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, pentyl group, isopentyl group, neopentyl group, Hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, eicosyl, heicosyl Derived from a linear or branched alkyl group having 3 to 30 carbon atoms such as heicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, triacontyl group, etc. One or more hydrogen atoms of the monovalent hydrocarbon group Hydroxy group, a halogen atom, a nitro group, a carboxyl group, an optionally substituted alkyl group, an aralkyl group or a substituted group with an alkoxy group.

Further, in X ² in the formula (1), the monovalent cyclic saturated or unsaturated hydrocarbon group having 3 to 30 carbon atoms, alicyclic hydrocarbons and aromatic hydrocarbons having 3 to 30 carbon atoms Examples include derived groups.

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

  Examples of the aromatic hydrocarbon include benzene, naphthalene, anthracene and the like.

  Preferred monomers that give the structural moiety represented by the above formula (1) include 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isobornyl (meth) acrylate. And monofunctional (meth) acrylate compounds such as adamantyl (meth) acrylate.

As a commercial product of a monomer that gives a structural site represented by the above formula (1),
Light Ester (registered trademark) EH, ID, L, S, IB-X (above, manufactured by Kyoeisha Chemical Co., Ltd.);
Light acrylate (registered trademark) LA, SA, IB-XA (above, manufactured by Kyoeisha Chemical Co., Ltd.);
Sartomer (registered trademark) SR242, SR313, SR324, SR423, SR493D, SR257, SR335, SR395, SR440, SR489D, SR506 (above, manufactured by Sartomer);
Blemmer (registered trademark) EHMA-25, LMA, SLMA, PMA, CMA, SMA, LA, CA, SA (above, NOF Corporation);
Acryester (registered trademark) EH, L, S, TD (Mitsubishi Rayon Co., Ltd.);
MADA, MADMA, EtADA, EAMA (P) (manufactured by Osaka Organic Chemical Industry Co., Ltd.);
Etc.

Y ¹ in the above formula (2) represents a hydrogen atom or a monovalent linear or branched saturated hydrocarbon group having 1 to 3 carbon atoms, and a monovalent linear chain having 1 to 3 carbon atoms. Or as a branched saturated hydrocarbon group, a methyl group, an ethyl group, 1-propyl group, 2-propyl group etc. can be mentioned, for example. And, it preferred Y ¹ in the formula (2), a hydrogen atom, methyl group.

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

Examples of the divalent linear or branched saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms in Y ² of the above formula (2) include, for example, methyl group, ethyl group, n-propyl group, i -Propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, Examples thereof include a divalent hydrocarbon group derived from a linear or branched alkyl group having 1 to 12 carbon atoms such as an undecyl group or a dodecyl group.

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

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

  Examples of the aromatic hydrocarbon include benzene and naphthalene.

As described above, the divalent linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms in Y ² of the formula (2) is a divalent linear chain. One or more hydrogen atoms of a straight, branched or cyclic saturated or unsaturated hydrocarbon group, a hydroxy group, a halogen atom, a nitro group, a carboxyl group, an alkyl group which may have a substituent, an aralkyl group, or It may be a group substituted with an alkoxy group.

Examples of the divalent organic group in Y ³ of the above formula (2) include a divalent aliphatic group and a divalent aromatic group. Further, as the divalent organic group, “a non-condensed polycyclic aromatic group in which aromatic groups are connected to each other directly or via a connecting group” can be exemplified. Examples of the linking group in that case include —O—, —CO—, —S—, —SO ₂ —, an alkylene group, and —C (CF ₃ ) ₂ —.

  Examples of the divalent aliphatic group include a divalent linear, branched or cyclic saturated or unsaturated hydrocarbon group. In that case, the linear, branched or cyclic saturated or unsaturated hydrocarbon group may be a group in which a hetero atom such as oxygen, nitrogen, sulfur and chlorine is bonded to the carbon chain in addition to hydrogen. Accordingly, a divalent straight chain, branched or cyclic saturated or unsaturated hydrocarbon group is one or more hydrogen atoms of a divalent straight chain, branched or cyclic saturated or unsaturated hydrocarbon group. It may be a group substituted by a hydroxy group, a halogen atom, a nitro group, a carboxyl group, an alkyl group which may have a substituent, an aralkyl group or an alkoxy group.

  Examples of the divalent linear or branched saturated or unsaturated hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and 2-methyl. 1 to 12 carbon atoms such as propyl, 1-methylpropyl, t-butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl And a divalent hydrocarbon group derived from a linear or branched alkyl group.

  In addition, examples of the divalent cyclic saturated or unsaturated hydrocarbon group that is the divalent aliphatic group described above include groups derived from alicyclic hydrocarbons.

Examples of the alicyclic hydrocarbon include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, cyclododecane, bicyclo [1.1.0] butane, and bicyclo [2.1. 0.0] pentane, bicyclo [2.2.0] hexane, bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, tricyclo [5.2.1.0 ^2,6 ] decane, And cycloalkanes such as tricyclo [3.3.1.1 ^3,7 ] decane.

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

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

  The divalent aromatic group is an alkyl group or aralkyl group in which one or more hydrogen atoms of the divalent aromatic group may have a hydroxy group, a halogen atom, a nitro group, a carboxyl group, or a substituent. Or a group substituted with an alkoxy group.

  Examples of the above-mentioned “non-condensed polycyclic aromatic group in which aromatic groups are linked to each other directly or via a linking group” include groups derived from biphenyl, phenyl ether, benzophenone, diphenyl sulfone, diphenyl sulfide and the like. It is done.

When n in the formula (2) it is 1, the structural moiety represented by the above formula (2) can be seen to include a structure in which two carboxyl groups are bonded to Y ^3. That is, when n in the formula (2) is 1, Y ^3, and two carboxyl groups attached respectively to Y ³ forms a dicarboxylic acid structure.

In that case, Y ^3, and two carboxyl groups attached respectively to Y ^3, as described above, for example, aliphatic dicarboxylic acid structure, and it is possible to form an aromatic dicarboxylic acid structure. Further, Y ^3, and two carboxyl groups attached respectively to Y ³ are "an aromatic group is directly or, for example, mutually linked non-condensed polycyclic aromatic group by a linking group as described above," the Including dicarboxylic acid structures can also be formed.

  More specifically, as the aliphatic dicarboxylic acid structure, for example, a malonic acid structure, a succinic acid structure, a glutaric acid structure, an adipic acid structure, a pimelic acid structure, a suberic acid structure, an azelaic acid structure, a sebacic acid structure, etc. Saturated dicarboxylic acid structure; aliphatic unsaturated dicarboxylic acid structure such as maleic acid structure, fumaric acid structure, itaconic acid structure, mesaconic acid structure, citraconic acid structure; hexahydrophthalic acid structure, hexahydroisophthalic acid structure, hexahydroterephthalic acid Structures, alicyclic dicarboxylic acid structures such as 4-methylcyclohexanedicarboxylic acid structures can be formed.

  Further, as an aromatic dicarboxylic acid structure, or a dicarboxylic acid structure containing an “non-condensed polycyclic aromatic group in which aromatic groups are directly or mutually connected by the above-described connecting groups”, for example, Phthalic acid structure, 2,3-benzophenone dicarboxylic acid structure, 3,4-benzophenone dicarboxylic acid structure, 2,3-dicarboxyphenyl phenyl ether structure, 3,4-dicarboxyphenyl phenyl ether structure, 2,3-biphenyl dicarboxylic acid Acid structure, 3,4-biphenyl dicarboxylic acid structure, 2,3-dicarboxyphenyl phenyl sulfone structure, 3,4-dicarboxyphenyl phenyl sulfone structure, 2,3-dicarboxyphenyl phenyl sulfide structure, 3,4-di Carboxyphenyl phenyl sulfide structure, 1,2-naphthalenedicarbo Dicarboxylic acids such as acid structure, 2,3-naphthalenedicarboxylic acid structure, 1,8-naphthalenedicarboxylic acid structure, 1,2-anthracene dicarboxylic acid structure, 2,3-anthracene dicarboxylic acid structure, 1,9-anthracene dicarboxylic acid structure An acid structure can be formed.

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

Examples of the monovalent linear or branched saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms in Y ⁴ of the above formula (2) include, for example, methyl group, ethyl group, n-propyl group, i -Propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, Examples thereof include monovalent hydrocarbon groups derived from a linear or branched alkyl group having 1 to 12 carbon atoms such as an undecyl group and a dodecyl group.

The monovalent cyclic saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms in Y ⁴ in the above formula (2) is derived from alicyclic hydrocarbons and aromatic hydrocarbons having 3 to 12 carbon atoms. Groups.

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

  Examples of the aromatic hydrocarbon include benzene and naphthalene.

As described above, the monovalent linear, branched, or cyclic saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms in Y ⁴ in the formula (2) is a monovalent linear chain. One or more hydrogen atoms of a straight, branched or cyclic saturated or unsaturated hydrocarbon group, a hydroxy group, a halogen atom, a nitro group, a carboxyl group, an alkyl group which may have a substituent, an aralkyl group, or It may be a group substituted with an alkoxy group.

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

  Preferred monomers that give the structural moiety represented by the above formula (2) include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, ω-carboxy-polycaprolactone monoacrylate, 2-methacryloyl Examples include (meth) acrylate compounds such as loxyethyl hexahydrophthalic acid.

As a commercially available product of a preferable monomer that gives a structural site represented by the above formula (2),
Light Ester (registered trademark) HO-MS, HO-HH (manufactured by Kyoeisha Chemical Co., Ltd.);
Light acrylate (registered trademark) HOA-MS, HOA-HH, HOA-MPL (manufactured by Kyoeisha Chemical Co., Ltd.);
Etc.

  [A] molar ratio of the content of the structural moiety represented by the above formula (1) and the structural moiety represented by the above formula (2) in the polymer ((structural moiety (1)) / (structural moiety (2))) Is preferably (structural part (1)) / (structural part (2)) = 1/3 to 5/1, and (structural part (1)) / (structural part (2)) = 3 More preferably, the ratio is / 5 to 3/1. And the sum total of content of the structure part (1) in a [A] polymer and a structure part (2) is 5 mol%-when the sum total of all the structure parts in a [A] polymer is 100 mol%. It is preferably 100 mol%, more preferably 5 mol% to 95 mol%, and still more preferably 10 mol% to 90 mol%.

  When the content of the structural site (1) and the structural site (2) is 5 mol% or more of the total of all the structural sites in the above-described molar ratio, the [A] polymer is [B] quantum dots. It can be a resin component that realizes a good dispersion state.

  [A] polymer demonstrated above is contained in the curable resin composition of 1st Embodiment of this invention, and is melt | dissolved or disperse | distributed. And the resin composition for obtaining the layer and film | membrane containing a [B] quantum dot can be formed using simple formation methods, such as application | coating.

[[B] quantum dots]
[B] Quantum dots, which are essential components of the curable resin composition of the first embodiment of the present invention, are preferably semiconductor quantum dots configured using a semiconductor material. The [B] quantum dot is preferably a quantum dot made of a safe material that does not contain Cd and Pb as constituents, and is composed of, for example, In (indium) or Si (silicon). .

  Accordingly, [B] quantum dots are at least two or more selected from the group of elements represented by Group 2 elements, Group 11 elements, Group 12 elements, Group 13 elements, Group 14 elements, Group 15 elements and Group 16 elements. A quantum dot made of a compound containing an element is preferable.

  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 It is preferably a quantum dot made of a compound containing at least two elements selected from the group consisting of (sulfur), Se (selenium), Te (tellurium) and Po (polonium).

  At this time, it is preferable that [B] quantum dot consists of a compound (a) which has a fluorescence maximum in the wavelength range of 500 nm-600 nm and / or a compound (b) which has a fluorescence maximum in the wavelength range of 600 nm-700 nm.

  [B] The quantum dot is composed of the compound (a) and / or the compound (b) having such fluorescence emission characteristics, so that the quantum dot is fluorescent in a wavelength region of 500 nm to 600 nm and / or a wavelength region of 600 nm to 700 nm. Can have a maximum. As a result, the curable resin composition according to the first embodiment of the present invention containing [B] quantum dots is a cured film suitable for the structure of the light emitting layer of a light emitting device that displays an image using light in the visible range. Can be formed.

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

  [B] As the quantum dot, Si or Si compound is particularly preferable.

  [B] By making the component configuration of the quantum dots as described above, the curable resin composition of the first embodiment of the present invention can form a cured film that is safe and has excellent fluorescence characteristics. Furthermore, it is possible to form a wavelength conversion film that is safe and has excellent fluorescence characteristics, and a light emitting layer of a light emitting element.

  [B] Quantum dots contained in the curable resin composition of the first embodiment of the present invention are selected from a homogeneous structure type composed of one compound and a core-shell structure type composed of two or more compounds. It is preferable that the quantum dots have at least one structure type.

  The [B] quantum dot of the core-shell structure type is configured 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 dots is reduced, and the quantum yield of light emission and the stability of the fluorescence characteristics of [B] quantum dots are improved.

[B] Quantum dots contained in the curable resin composition of the first embodiment of the present invention are InP / ZnS, CuInS ₂ / ZnS, which are core-shell structured quantum dots, in view of the component structure and structure. It is preferably at least one selected from the group consisting of ZnS / AgInS ₂ ) solid solution / ZnS, and AgInS ₂ which is a homogeneous structure type quantum dot and Zn-doped AgInS ₂ .

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

  The curable resin composition according to the first embodiment of the present invention containing the [B] quantum dots exemplified above forms a cured film having a safer and more excellent fluorescence property, and more A wavelength conversion film having excellent fluorescence characteristics and a light emitting layer of a light emitting element can be formed.

  The [B] quantum dots contained in the curable resin composition of the first embodiment of the present invention preferably have an average particle diameter of 0.5 nm to 20 nm, and preferably 1.0 nm to 10 nm. More preferred. When the average particle size is less than 0.5 nm, it is difficult to prepare [B] quantum dots, and even if it can be prepared, the fluorescence characteristics of [B] quantum dots may become unstable. [B] When the average particle diameter of the quantum dots exceeds 20 nm, the quantum confinement effect due to the size of the quantum dots may not be obtained, and the desired fluorescence characteristics cannot be obtained, which is not desirable.

  Moreover, the shape of [B] quantum dots 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 for obtaining [B] quantum dots contained in the curable resin composition of the first embodiment of the present invention, a known method of thermally decomposing an organometallic compound in a coordinating organic solvent may be used. it can. In addition, core-shell type quantum dots form a homogeneous core structure by reaction, then add a precursor to form a shell on the core surface in the reaction system, and stop the reaction after shell formation. It can be obtained by separating from a solvent. A commercially available product can also be used.

  The content of [B] quantum dots in the curable resin composition of the first embodiment of the present invention is preferably 0.1 parts by mass to 100 parts by mass with respect to 100 parts by mass of the above-described [A] component. More preferably, it is 0.2 mass part-50 mass parts. [B] By setting the content of quantum dots within 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 a light emitting element are formed. Can do. [B] If the content of the quantum dots is less than 0.1 parts by mass with respect to 100 parts by mass of the component [A], the desired fluorescence characteristics cannot be obtained in the formed cured film, and wavelength conversion is performed. A light emitting layer of a 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 [A] component, the 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.

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

  The curable resin composition of 1st Embodiment of this invention can improve radiation sensitivity and can improve patternability by containing a [C] polymerization initiator. And the curable resin composition of 1st Embodiment of this invention can form the light emitting layer and wavelength conversion film which were patterned easily using well-known patterning methods, such as the photolithographic method. [C] The polymerization initiator is used together with the [D] polymerizable unsaturated compound described later, and is preferably contained in the curable resin composition of the first embodiment of the present invention. Thereby, the curable resin composition of the first embodiment of the present invention can further improve the crosslinking reactivity, and the cured film of the second embodiment of the present invention formed from this curable resin composition. The film strength and the adhesion to the substrate can be further enhanced.

  In the curable resin composition of the first embodiment of the present invention, examples of the [C] polymerization initiator include oxime ester compounds, acetophenone compounds, biimidazole compounds, and the like. In addition, you may use [C] polymerization initiator individually or in combination of 2 or more types.

  Examples of the oxime ester compound include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1,2-octane. Dione-1- [4- (phenylthio) -2- (O-benzoyloxime)], 1- [9-ethyl-6-benzoyl-9H-carbazol-3-yl] -octane-1-oneoxime-O-acetate 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2- Ethylbenzoyl) -9H-carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone-1- [9-ethyl-6- (2-methyl-4-teto) Hydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9H- Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl] O-acyloxime compounds such as -1- (O-acetyloxime) and the like can be mentioned.

  Among the oxime ester compounds described above, etanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1,2 -Octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazole -3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl}- 9H-carbazol-3-yl] -1- (O-acetyloxime) is preferred.

  Examples of the acetophenone compound include α-aminoketone compounds.

  Examples of the α-aminoketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and 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 can be mentioned.

  The acetophenone compound is preferably an α-aminoketone compound, such as 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2- More preferred is methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one.

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

  [C] As the polymerization initiator, a commercially available product may be used. For example, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (Irgacure (registered trademark) 907) 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -butan-1-one (Irgacure 379), 1,2-octanedione-1- [4- ( Phenylthio) -2- (O-benzoyloxime)] (Irgacure (registered trademark) OXE01), ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (Irgacure (registered trademark) OXE02) (manufactured by BASF Japan Ltd.).

  Furthermore, the [C] polymerization initiator is preferably a polymerization initiator having no nitrogen atom in the molecule. By using the [C] polymerization initiator having such a structure, the curable resin composition of the first embodiment of the present invention has the cured film of the second embodiment of the present invention having more excellent fluorescence characteristics. Can be formed.

  Specific examples of the polymerization initiator having no nitrogen atom in the molecule include 2,2-dimethoxy-1,2-diphenylethane-1-one (Irgacure (registered trademark) 651), 1- Hydroxycyclohexyl phenyl ketone (Irgacure® 184), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Irgacure® 1173), 1- [4- (2-hydroxyethoxy) -Phenyl] -2-hydroxy-2-methyl-1-propan-1-one (Irgacure® 2959), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) ) -Benzyl] phenyl} -2-methyl-propan-1-one (Irgacure® 127), phenylglyoxylic Cyd methyl ester (Darocur® MBF), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (LUCIRIN® TPO), bis (2,4,6-trimethylbenzoyl) -phenylphosphine And oxide (Irgacure (registered trademark) 819).

  [C] As content of a polymerization initiator, 0.1 mass part-40 mass parts are preferable with respect to 100 mass parts of [A] component, and 0.5 mass part-20 mass parts are more preferable. [C] By setting the content of the polymerization initiator in the above range, the curable resin composition of the first embodiment of the present invention exhibits good patternability even in the case of a low exposure amount, and has a sufficient surface. A cured film having hardness and adhesion can be formed.

[[D] polymerizable unsaturated compound]
The curable resin composition of the first embodiment of the present invention can further contain [D] a polymerizable unsaturated compound. The [D] polymerizable unsaturated compound contained in the curable resin composition of the first embodiment of the present invention is a compound having a polymerizable unsaturated structure. Crosslinking reactivity can be improved because the curable resin composition of 1st Embodiment of this invention contains a [D] polymerizable unsaturated compound. And the film | membrane intensity | strength of the cured film of 2nd Embodiment of this invention formed from this curable resin composition and adhesiveness with a board | substrate can be improved. In that case, [D] a polymerizable unsaturated compound is used with the [C] polymerization initiator mentioned above, and it is preferable to contain in the curable resin composition of 1st Embodiment of this invention.

  Such a [D] polymerizable unsaturated compound is a monofunctional, bifunctional, or trifunctional (meth) acrylic acid ester from the viewpoint of good polymerizability and improved strength of the resulting cured film. Is preferred.

  Examples of the monofunctional (meth) acrylic acid ester described above include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether acrylate, diethylene glycol monoethyl ether methacrylate, (2-acryloyloxyethyl) (2-hydroxy Propyl) phthalate, (2-methacryloyloxyethyl) (2-hydroxypropyl) phthalate, ω-carboxypolycaprolactone monoacrylate and the like. Examples of commercially available products include, for example, Aronix M-101, M-111, M-114, M-5300 (above, manufactured by Toagosei Co., Ltd.); KAYARAD TC-110S, TC-120S (above, Nippon Kayaku) Biscoat 158, 2311 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) and the like.

  Examples of the bifunctional (meth) acrylic acid ester include ethylene glycol diacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, and tetraethylene glycol. Examples include dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, and the like. As a commercial item, for example, Aronix (registered trademark) M-210, M-240, M-6200 (above, manufactured by Toagosei Co., Ltd.); KAYARAD (registered trademark) HDDA, HX-220, R-604 (Nippon Kayaku Co., Ltd.); Biscoat 260, 312 and 335HP (Osaka Organic Chemical Industries, Ltd.); Light Acrylate (registered trademark) 1,9-NDA (Kyoeisha Chemical Co., Ltd.)

Examples of the tri- or more functional (meth) acrylic acid ester include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, and ditrimethylolpropane. Tetraacrylate, ditrimethylolpropane tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethylene oxide Modified dipentaerythritol hexaacrylate, tri (2-acryloyloxyethyl) phosphate, tri (2-methacryloyloxyethyl) phosphate, succinic acid modified pentaerythritol triacrylate, succinic acid modified dipentaerythritol pentaacrylate, A compound having a chain alkylene group and an alicyclic structure and having two or more isocyanate groups, one or more hydroxyl groups in the molecule, and 3, 4, or 5 (meth) Examples thereof include polyfunctional urethane acrylate compounds obtained by reacting with a compound having an acryloyloxy group. Examples of commercially available products include Aronix (registered trademark) M-309, M-400, M-405, M-450, M-7100, M-8030, M-8060, and TO-1450. (Above, manufactured by Toagosei Co., Ltd.); KAYARAD (registered trademark) TMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-60, DPCA-120, DPEA-12 (above, Nippon Kayaku Co., Ltd.) ); Biscoat (registered trademark) 295, 300, 360, GPT, 3PA, 400 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.); As a commercial product containing a polyfunctional urethane acrylate compound, New Frontier (Registered Trademark) R-1150 (Daiichi Kogyo Seiyaku Co., Ltd.), KAYARAD (Registered Trademark) DPHA-40H (Nihon Kayaku Co., Ltd.) and the like can be mentioned.

  Among these [D] polymerizable unsaturated compounds, ω-carboxypolycaprolactone monoacrylate, 1,9-nonanediol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetra Acrylate, ditrimethylolpropane tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, ethylene oxide modified dipentaerythritol hexaacrylate, succinic acid modified pentaerythritol Triacrylate, succinic acid modified dipentaerythritol Printer acrylate, including commercial products containing multifunctional urethane acrylate compounds are preferable.

  The above-mentioned [D] polymerizable unsaturated compound may be used alone or in combination of two or more. The proportion of the [D] polymerizable unsaturated compound used in the curable resin composition of the first embodiment of the present invention is preferably 30 parts by mass to 250 parts by mass with respect to 100 parts by mass of the component [A]. Mass parts to 200 parts by mass are more preferable. [D] When the usage-amount of a polymerizable unsaturated compound is 30 mass parts-250 mass parts, the sensitivity of the curable resin composition of 1st Embodiment of this invention and the heat resistance of the cured film obtained become more favorable. .

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

  As a preferable [E] antioxidant as a component of the curable resin composition of 1st Embodiment of this invention, a phosphite type antioxidant can be mentioned. The phosphite antioxidant comprises a compound having a phosphite structure. In addition, examples of the [E] antioxidant include a phenol compound, a compound having a hindered phenol structure, a compound having a hindered amine structure, and a compound having a thioether structure.

  Examples of phosphite antioxidants include tris (2,4-di-tert-butylphenyl) phosphite and bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester. Phosphorous acid, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl) -4-methylphenyl) pentaerythritol-di-phosphite, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tri (o-tolyl) phosphine, tri (p-tolyl) List phosphine, cyclohexyldiphenylphosphine, ethyldiphenylphosphine, etc. It can be. Examples of commercially available products include ADK STAB (registered trademark) PEP-36, PEP-4C, PEP-8, PEP-8F, PEP-8W, PEP-11C, PEP-24G, and HP-10. 2112, 260, ADK STAB (registered trademark) P, ADK STAB (registered trademark) QL, 522A, 329K, 1178, 1500, ADK STAB (registered trademark) C, 135A, 3010, ADK STAB (registered trademark) ) TPP (above, manufactured by Adeka), Irgafos (registered trademark) 38, Irgafos (registered trademark) 168, Irgafos (registered trademark) P-EPQ (all of which are manufactured by BASF Japan).

  Of these, phosphite antioxidants having an aromatic group represented by the following formula are particularly preferred.

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

The R _B, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl, 2-methylpropyl group, 1-methylpropyl group, t- butyl group, a pentyl group, isopentyl group, neopentyl Group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group, xylyl group, naphthyl group and the like.
As R _C , methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, pentyl group, isopentyl group, neopentyl group Group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, eicosyl group, Henicosyl group, heicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, triacontyl group, phenyl group, tolyl group, xylyl group, naphthyl group, etc. 30 linear or branched alkyl groups Derived hydrocarbon groups can be mentioned.

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

  Examples of the compound having the hindered phenol structure described above include 2,6-di-tert-butyl-4-cresol, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl). Propionate], thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N′-hexane-1,6-diylbis [3- (3 , 5-di-tert-butyl-4-hydroxyphenylpropionamide)], 3,3 ′, 3 ″, 5 ′, 5 ″ -hex -Tert-butyl-a, a ', a' '-(mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, 4,6- Bis (dodecylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5- Di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4 6 (1H, 3H, 5H) -trione, 1,3,5-tris [(4-tert-butyl-3-hydroxy-2,6-xylin) methyl] -1,3,5-triazine-2 4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamine) phenol, tris -(3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate and the like.

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

  Examples of commercially available compounds having a hindered amine structure include, for example, ADK STAB (registered trademark) LA-52, LA57, LA-62, LA-67, LA-63P, LA-68LD, LA-77, LA-82, LA-87 (manufactured by Adeka), sumilizer (registered trademark) 9A (manufactured by Sumitomo Chemical), CHIMASSORB (registered trademark) 119FL, 2020FDL, 944FDL, TINUVIN (registered trademark) 622LD, 144, 765, and 770DF (manufactured by BASF Japan Ltd.).

  Examples of commercially available compounds having a thioether structure include ADK STAB (registered trademark) AO-412S, AO-503 (manufactured by Adeka), Sumilizer (registered trademark) TPL-R, TPM, TPS, TP-D, MB (above, manufactured by Sumitomo Chemical Co., Ltd.), IRGANOX (registered trademark) PS800FD, PS802FD (above, manufactured by BASF Japan), DLTP, DSTP, DMTP, DTTP (above, manufactured by API Corporation), etc. Is mentioned.

  [E] Antioxidants may be used alone or in admixture of two or more. As content of [E] antioxidant in the curable resin composition of 1st Embodiment of this invention, Preferably it is 0.1 mass part-10 mass parts with respect to 100 mass parts of [A] component. Preferably they are 0.2 mass part-5 mass parts. [E] By setting the content of the antioxidant in the above range, the transmittance and heat-resistant transparency of the cured film of the second embodiment of the present invention obtained from the curable resin composition of the first embodiment of the present invention. The sex can be further improved.

[Other optional ingredients]
The curable resin composition of the first embodiment of the present invention contains the [A] component and [B] quantum dots as essential components, and contains other optional components as long as the effects of the present invention are not impaired. be able to. Examples of other optional components include a solvent, a curing accelerator, and a thermal acid generator.

  The curing accelerator is a compound that functions to promote curing of a film formed by the curable resin composition of the present embodiment.

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

  Furthermore, the curable resin composition of the present embodiment is within a range that does not impair the effects of the present invention, and other optional components such as a surfactant, a storage stabilizer, an adhesion aid, and a heat resistance improver, if necessary. Can be contained. Each of these optional components may be used alone or in combination of two or more.

[Method for preparing curable resin composition]
The curable resin composition of 1st Embodiment of this invention is prepared by mixing a [A] polymer and a [B] quantum dot uniformly. In addition, when the optional [C] component, [D] component, and [E] component are included, the [C] component and [D] as necessary together with the [A] component and [B] component It is prepared by mixing the components and [E] component uniformly.

  Furthermore, when other optional components described above are selected as necessary, and they are contained, they are prepared by uniformly mixing the other optional components together with the [A] component and the [B] component. .

  And in preparing the curable resin composition of 1st Embodiment of this invention, in order to prepare the curable resin composition of a dispersion state, an organic solvent can be used.

  As a function of the organic solvent, for example, the viscosity of the curable resin composition of the first embodiment of the present invention is adjusted, for example, to improve applicability to a substrate or the like, and to improve operability and moldability. And so on.

  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 include nates, hydrocarbons, ketones, and esters.

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 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.

  A hydrocarbon solvent is preferable from the viewpoint of the dispersibility of the quantum dots. Examples of the hydrocarbon include an aromatic hydrocarbon solvent and an aliphatic hydrocarbon solvent. Examples of the aromatic hydrocarbon solvent include toluene, ethylbenzene, amylbenzene, isopropylbenzene, xylene, cyclohexylbenzene, naphthalene, dimethylnaphthalene, cymene, tetralin, biphenyl, mesitylene and the like. Aliphatic hydrocarbon solvents include hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, methylcyclohexane, ethylcyclohexane, p-menthane, decalin, isooctane, isododecane, cyclohexene, cyclopentane, dipentene, isoper E , Isopar G, Isopar H, Isopar L, Isopar M (manufactured by Ogura Kosan Co., Ltd.), turpentine oil, decahydronaphthalene, limonene, benzine, Kyowasol C-800, shellzol, Isosol, Ligroin (Gordo Kogyo Co., Ltd.) Etc.).

  Among these organic solvents, ethers such as dialkyl ethers, diethylene glycol alkyl ethers, ethylene glycol from the viewpoint of excellent solubility, non-reactivity with each component, and ease of film formation. 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 monoether 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.

  In addition to the organic solvents 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 in the curable resin composition of the first embodiment of the present invention 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 (components other than the solvent component in the curable resin composition solution) can be arbitrarily set according to the purpose of use, desired film thickness, and the like. However, it is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, and still more preferably 15% by mass to 35% by 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 is formed by applying the above-described curable resin composition of the first embodiment of the present invention on a substrate, patterning if necessary, and then heat curing. The Below, the cured film and its formation method of 2nd Embodiment of this invention are demonstrated.

  In the formation method of forming the cured film of the second embodiment of the present invention, at least the following steps (1) to (4) may be included in the following order so that the cured film is formed on the substrate. preferable.

(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 exposing the coating film developed in step (3).

  1 to 4 are diagrams for explaining an example of 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 an example of a coating film forming step in forming a cured film according to the second embodiment of the present invention.

  FIG. 2 is a cross-sectional view schematically illustrating an example of 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 an example of a developing 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 an example of 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 of the second embodiment of the present invention, as illustrated in FIG. 1, the curable resin composition of the first embodiment of the present invention A coating film 1 is formed on the substrate 2.

  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 first embodiment of the present invention is applied to one surface, prebaking is performed, and components such as an organic solvent contained in the curable resin composition are evaporated. The coating film 1 is formed.

  Examples of the coating method of the curable resin composition of the first embodiment of the present invention in this step include a spray method, a roll coating method, and a spin coating method (sometimes referred to as a spin coating method or a spinner method). An appropriate method such as a slit coating method (slit die coating method), a bar coating method, or an ink jet coating method can be employed. 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 step which is the step (2) of the formation method of the cured film of the second embodiment of the present invention, as illustrated in FIG. 2, the coating formed on the substrate 2 in the step (1). At least a part of the film 1 is irradiated with radiation 4. At this time, in order to irradiate only a part of the coating film 1 with the radiation 4a, 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 the step (3) of the formation method of the cured film of the second embodiment of the present invention, the coating film 1 of FIG. 2 after irradiation is developed as illustrated in FIG. Then, unnecessary portions are removed, and 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 addition of 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 the step (4) of the formation method of the cured film of the second embodiment of the present invention, the patterned coating film 1a illustrated in FIG. 3 is exposed by exposure using an exposure apparatus. Curing (also called post-exposure). Thereby, as illustrated in FIG. 4, a cured film 5 that is an example of the second embodiment of the present invention formed on the substrate 2 is obtained. As described above, the cured film 5 is patterned so as to have a desired shape.

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

Examples of the ultraviolet rays include g-line (wavelength 436 nm), i-line (wavelength 365 nm), and the like. Examples of the far ultraviolet light include KrF excimer laser light. Examples of X-rays include synchrotron radiation. Examples of the charged particle beam include an electron beam. Of these radiations, the use of ultraviolet rays is preferable, and among the ultraviolet rays, radiation containing at least one of g-line, h-line and i-line is more preferable. The exposure dose of radiation is preferably 0.1 J / m ^{2 to} 30000 J / m ² .

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

  Moreover, it is also possible to provide the light emitting element of 4th Embodiment of this invention using the cured film of 2nd Embodiment of this invention as a light emitting layer. In that case, the light emitting layer which the light emitting element of 4th Embodiment of this invention has uses the curable resin composition of 1st Embodiment of this invention, and forms the cured film of 2nd Embodiment of this invention mentioned above. According to the formation method, it can form similarly. And the light emitting layer of the light emitting element of 4th Embodiment of this invention has the fluorescence light emission (wavelength conversion) function based on a [B] quantum dot.

  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.

  Therefore, the cured film of the second embodiment of the present invention preferably has a total light transmittance (JIS K7105) at a thickness of 0.1 mm in the resin constituting the cured film so that the light use efficiency can be increased. Is 75% to 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.
<Wavelength conversion film>
As described above, the cured film of the second embodiment of the present invention includes [B] quantum dots in the resin based on the [A] polymer of the curable resin composition of the first embodiment of the present invention. Consists of. And the cured film of 2nd Embodiment of this invention has the fluorescence light emission (wavelength conversion) function based on the [B] quantum dot contained. Therefore, the cured film of 2nd Embodiment of this invention can be used as a wavelength conversion film of 3rd Embodiment of this invention which light-emits the fluorescence of a wavelength different from excitation light.

  Therefore, the wavelength conversion film of 3rd Embodiment of this invention uses the curable resin composition of 1st Embodiment of this invention, and forms the cured film of 2nd Embodiment of this invention mentioned above according to the formation method. Can be formed. And the wavelength conversion film of 3rd Embodiment of this invention has a fluorescence light emission (wavelength conversion) function based on a [B] quantum dot.

  The wavelength conversion film of 3rd Embodiment of this invention can be used with a color liquid crystal display panel, for example, and can provide a color liquid crystal display element. In that case, for example, the wavelength conversion film of the third embodiment of the present invention is arranged on a known color liquid crystal display panel, and a color liquid crystal display element capable of high color purity color display can be provided. That is, the wavelength conversion film according to the third embodiment of the present invention can be used to improve the color purity of the display that the color liquid crystal display panel originally has, and the color liquid crystal that further improves the color purity of the display. A display element can be provided.

Embodiment 4 FIG.
<Formation of light emitting 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.

  That is, the light emitting device of the fourth embodiment of the present invention uses the cured film of the second embodiment of the present invention as a wavelength conversion film or a light emitting layer, and can constitute, for example, a light emitting display device or the like. it can. And the light emitting display element which is an example of 4th Embodiment of this invention can be comprised using the wavelength conversion board | substrate which has the cured film of 2nd Embodiment of this invention mentioned above as a light emitting layer, for example. In the light emitting device of the fourth embodiment of the present invention, the light emitting layer can be formed according to the method of forming a light emitting layer of the fifth embodiment of the present invention.

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

  The light emitting display element 100 as an example of the fourth 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. And a light source substrate 18 bonded to the substrate 11 via 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 uses 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 the light emitting layer which is 5th Embodiment of this invention, since the light emitting layer utilizes the cured film of 2nd Embodiment of this invention, 2nd Embodiment of this invention mentioned above. This is the same as the forming method of forming the cured film. 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 exposing 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 the quantum dots contained therein, converts the wavelength of the excitation light from the excitation light source 17 of the light source substrate 18, and emits fluorescence having a desired wavelength.

  In the wavelength conversion substrate 11, the light emitting layer 13a, the light emitting layer 13b, and the light emitting layer 13c of the light emitting layer 13 are configured to include different quantum dots, and can 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 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 types of the curable resin composition of the first embodiment including 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 which is an example of 4th Embodiment of this invention converts the wavelength of the excitation light from the light source 17a which is one of the light sources 17 with the quantum dot of the light emitting layer 13a of the wavelength conversion board | substrate 11 which opposes. Similarly, the excitation light from the light source 17b is wavelength-converted by the quantum dots of the light emitting layer 13b of the opposing wavelength conversion substrate 11, and the excitation light from the light source 17c is converted to the light emitting layer 13c of the opposing wavelength conversion substrate 11 Wavelength conversion is performed by 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 can use a light scattering layer formed by dispersing light 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 obtained by patterning the light-emitting layer 13a, the light-emitting layer 13b, and the light-emitting layer 13c made of quantum dots and resin on the substrate 12, respectively. It is. The light emitting layers 13a, 13b, and 13c are each formed from the curable resin composition of the first embodiment of the present invention including 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 which is an example of the fourth embodiment of the present invention having the above-described configuration is provided for each sub pixel including the light emitting layer 13a, each sub pixel including the light emitting layer 13b, and each sub pixel including the light emitting layer 13c. The emission of red, green or blue light 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 as an example of the fourth 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 which is an example of 4th Embodiment of this invention can improve the purity of the color of a display 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.

<[A] polymer ([A] component)>
In this example, as an example of the above-mentioned [A] polymer, polymer (A-1), polymer (A-2), polymer (A-3), polymer (A-4) and polymer Combined (A-5) was used. Below, the synthesis example of a polymer (A-1)-a polymer (A-5) is shown.

Synthesis example 1
[Synthesis of Polymer (A-1)]
A flask equipped with a condenser and a stirrer was charged with 150 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same temperature, 50 parts by mass of propylene glycol monomethyl ether acetate, 30 parts by mass of 2-methacryloyloxyethyl succinic acid, 10 parts by mass of benzyl methacrylate, 60 parts by mass of 2-ethylhexyl methacrylate and 2,2 ′ -A mixed solution of 6 parts by mass of azobis (2,4-dimethylvaleronitrile) was added dropwise over 2 hours, and polymerization was carried out for 1 hour while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 90 ° C., and further polymerized for 1 hour to obtain a polymer (A-1). The polymer (A-1) was obtained in a state of a polymer solution (solid content concentration = 33% by mass), and Mw = 11000, Mn = 6100, and Mw / Mn = 1.80. This is referred to as a polymer (A-1) solution.

Synthesis example 2
[Synthesis of Polymer (A-2)]
A flask equipped with a condenser and a stirrer was charged with 150 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same temperature, 50 parts by mass of propylene glycol monomethyl ether acetate, 35 parts by mass of 2-methacryloyloxyethyl succinic acid, 65 parts by mass of 2-ethylhexyl methacrylate and 2,2′-azobis (2,4 -Dimethylvaleronitrile) A mixed solution of 6 parts by mass was dropped over 2 hours, and polymerization was carried out for 1 hour while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 90 ° C., and further polymerized for 1 hour to obtain a polymer (A-2). The polymer (A-2) was obtained in a state of a polymer solution (solid content concentration = 33% by mass), and Mw = 11300, Mn = 6000, and Mw / Mn = 1.88. This is referred to as a polymer (A-2) solution.

Synthesis example 3
[Synthesis of Polymer (A-3)]
A flask equipped with a condenser and a stirrer was charged with 150 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same temperature, 50 parts by mass of propylene glycol monomethyl ether acetate, 40 parts by mass of 2-methacryloyloxyethyl hexahydrophthalic acid, 20 parts by weight of benzyl methacrylate, 40 parts by mass of lauryl methacrylate and 2,2 ′ -A mixed solution of 6 parts by mass of azobis (2,4-dimethylvaleronitrile) was added dropwise over 2 hours, and polymerization was carried out for 1 hour while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 90 ° C., and further polymerized for 1 hour to obtain a polymer (A-3). The polymer (A-3) was obtained in a state of a polymer solution (solid content concentration = 33% by mass), and Mw = 11100, Mn = 6000, and Mw / Mn = 1.85. This is referred to as a polymer (A-3) solution.

Synthesis example 4
[Synthesis of Polymer (A-4)]
A flask equipped with a condenser and a stirrer was charged with 150 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same temperature, 50 parts by mass of propylene glycol monomethyl ether acetate, 40 parts by mass of 2-methacryloyloxyethyl hexahydrophthalic acid, 60 parts by mass of stearyl methacrylate and 2,2′-azobis (2,4 -Dimethylvaleronitrile) A mixed solution of 6 parts by mass was dropped over 2 hours, and polymerization was carried out for 1 hour while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 90 ° C., and further polymerized for 1 hour to obtain a polymer (A-4). The polymer (A-4) was obtained in a state of a polymer solution (solid content concentration = 33% by mass), and Mw = 12100, Mn = 6500, and Mw / Mn = 1.86. This is referred to as a polymer (A-4) solution.

Synthesis example 5
[Synthesis of Polymer (A-5)]
A flask equipped with a condenser and a stirrer was charged with 150 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same temperature, 50 parts by mass of propylene glycol monomethyl ether acetate, 40 parts by mass of 2-methacryloyloxyethyl succinic acid, 30 parts by weight of 2-ethylhexyl methacrylate, 30 parts by mass of isobornyl methacrylate and 2, A mixed solution of 6 parts by mass of 2′-azobis (2,4-dimethylvaleronitrile) was added dropwise over 2 hours, and polymerization was carried out for 1 hour while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 90 ° C., and further polymerized for 1 hour to obtain a polymer (A-4). The polymer (A-4) was obtained in a state of a polymer solution (solid content concentration = 33% by mass), and Mw = 11100, Mn = 6100, and Mw / Mn = 1.82. This is referred to as a polymer (A-5) solution.

<[B] Quantum dot ([B] component)>
The quantum dots used in this example are shown below.
Quantum dot A: InP / ZnS core-shell quantum dot quantum dot B: InCuS ₂ / ZnS core-shell quantum dot quantum dot C: Si quantum dot

The quantum dots A: InP / ZnS core-shell quantum dots, quantum dots B: InCuS ₂ / ZnS core-shell quantum dots, and quantum dots C: Si quantum dots used in the following examples are generally known methods. Can be synthesized.

For example, for the quantum dot A: InP / ZnS core-shell type quantum dot, the technical literature “Journal of American Chemical Society. 2007, 129, 15432-15433” and for the quantum dot B: InCuS ₂ / ZnS core-shell type quantum dot In “Journal of American Chemical Society. 2009, 131, 5691-5697” and in the technical document “Chemistry of Materials. 2009, 21, 2422-2429”, the technical document “JoChan et al. 2010, 132, 248-253 ”. Can be made.

  Using the above [A] polymer ([A] component) and [B] quantum dots, [C] polymerization initiator ([C] component), [D] polymerizable unsaturated compound ([D] component) ) Was used to prepare the curable resin compositions of the examples. Subsequently, the cured film of the Example was formed using them, and the cured film was evaluated.

Example 1
[Preparation of Curable Resin Composition (β-I)]
After adding 40 parts by mass of methylcyclohexane to 90 parts by mass of the polymer (A-1) solution, 10 parts by mass of quantum dots A are mixed to prepare a uniform solution, and 1,2-octanedione-1 -[4- (Phenylthio) -2- (O-benzoyloxime)] (BASF Japan Co., Ltd. Irgacure (registered trademark) OXE01) 10 parts by mass and 1,9-nonanediol diacrylate 70 parts by mass are mixed. A resin composition (β-I) was prepared.

Example 2
[Preparation of Curable Resin Composition (β-II)]
After adding 40 parts by mass of ethylcyclohexane to 90 parts by mass of the polymer (A-2) solution, 10 parts by mass of quantum dots B are mixed to prepare a uniform solution, and 1,2-octanedione-1 -[4- (Phenylthio) -2- (O-benzoyloxime)] (BASF Japan Co., Ltd. Irgacure (registered trademark) OXE01) 10 parts by mass and 1,10-decanediol diacrylate 60 parts by mass are mixed and cured. A resin composition (β-II) was prepared.

Example 3
[Preparation of Curable Resin Composition (β-III)]
After adding 40 parts by mass of p-menthane to 90 parts by mass of the polymer (A-3) solution, 10 parts by mass of quantum dots C are mixed to prepare a uniform solution, and 2-dimethylamino-2- 10 parts by mass of (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (Irgacure (registered trademark) 379 manufactured by BASF Japan Ltd.), 30 masses of ditrimethylolpropane tetraacrylate Parts were mixed to prepare a curable resin composition (β-III).

Example 4
[Preparation of Curable Resin Composition (β-IV)]
After adding 40 parts by mass of pinane to 90 parts by mass of the polymer (A-4) solution, 10 parts by mass of quantum dots A are mixed to prepare a uniform solution, and bis (2,4,6-trimethyl) 10 parts by mass of benzoyl) -phenylphosphine oxide (Irgacure (registered trademark) 819 manufactured by BASF Japan Ltd.), 5 parts by mass of tris (2,4-di-tert-butylphenyl) phosphite, 30 parts by mass of ditrimethylolpropane tetraacrylate Were mixed to prepare a curable resin composition (β-IV).

Example 5
[Preparation of Curable Resin Composition (β-V)]
After adding 40 parts by mass of methylcyclohexane to 90 parts by mass of the polymer (A-5) solution, 10 parts by mass of quantum dots A are mixed to prepare a uniform solution, and 2,2-dimethoxy-1, 25 parts by mass of 2-diphenylethane-1-one (Irgacure (registered trademark) 651, manufactured by BASF Japan Ltd.), 2 parts by mass of trisnonylphenyl phosphite, and 30 parts by mass of ditrimethylolpropane tetraacrylate are mixed to obtain a curable resin composition. (Β-V) was prepared.

Example 6
[Preparation of Curable Resin Composition (β-VI)]
After adding 40 parts by mass of methylcyclohexane to 90 parts by mass of the polymer (A-5) solution, 10 parts by mass of quantum dots A are mixed to prepare a uniform solution, and 1-hydroxycyclohexyl phenyl ketone (BASF) Japan Irgacure (registered trademark) 184) 25 parts by mass, ditrimethylolpropane tetraacrylate 30 parts by mass, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] 2 parts by mass Were mixed to prepare a curable resin composition (β-VI).

Example 7
[Formation of cured film using curable resin composition (β-I)]
A curable resin composition (β-I) prepared in Example 1 was applied onto an alkali-free glass substrate with a spinner, and then prebaked on an 80 ° C. hot plate for 2 minutes to form a coating film.

Next, radiation was applied to the obtained coating film through a photomask having a predetermined pattern at an exposure amount of 700 J / m ² using a high-pressure mercury lamp. Next, development was performed at 23 ° C. for 60 seconds with a 0.04 mass% potassium hydroxide aqueous solution.
Next, the obtained pattern was irradiated with radiation at an exposure amount of 10000 J / m ² using a high-pressure mercury lamp to form a cured film patterned into a predetermined shape.

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 (β-I) was good.

Example 8
[Formation of cured film using curable resin composition (β-II)]
The curable resin composition (β-II) prepared in Example 2 was applied on an alkali-free glass substrate with a spinner, and then pre-baked on an 80 ° 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 using a high pressure mercury lamp through a photomask having a predetermined pattern, and a 0.04 mass% potassium hydroxide aqueous solution was used. Development was performed at 23 ° C. for 60 seconds.
Next, the obtained pattern was irradiated with radiation at an exposure amount of 10000 J / m ² using a high-pressure mercury lamp to form a cured film patterned into a predetermined shape.

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 (β-II) was good.

Example 9
[Formation of cured film using curable resin composition (β-III)]
The curable resin composition (β-III) prepared in Example 3 was applied onto an alkali-free glass substrate with a spinner, and then pre-baked on an 80 ° 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 800 J / m ² using a high pressure mercury lamp through a photomask having a predetermined pattern, and a 0.04 mass% potassium hydroxide aqueous solution was used. Development was performed at 23 ° C. for 60 seconds.
Next, the obtained pattern was irradiated with radiation at an exposure amount of 10000 J / m ² using a high-pressure mercury lamp to form a cured film patterned into a predetermined shape.

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 (β-III) was good.

Example 10
[Formation of cured film using curable resin composition (β-IV)]
The curable resin composition (β-IV) prepared in Example 3 was applied onto an alkali-free glass substrate with a spinner, and then prebaked on an 80 ° 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 800 J / m ² using a high pressure mercury lamp through a photomask having a predetermined pattern, and a 0.04 mass% potassium hydroxide aqueous solution was used. Development was performed at 23 ° C. for 60 seconds.
Next, the obtained pattern was irradiated with radiation at an exposure amount of 10000 J / m ² using a high-pressure mercury lamp to form a cured film patterned into a predetermined shape.

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 (β-IV) was good.

Example 11
[Formation of cured film using curable resin composition (β-V)]
The curable resin composition (β-V) prepared in Example 3 was applied on an alkali-free glass substrate with a spinner, and then prebaked on an 80 ° 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 800 J / m ² using a high pressure mercury lamp through a photomask having a predetermined pattern, and a 0.04 mass% potassium hydroxide aqueous solution was used. Development was performed at 23 ° C. for 60 seconds.
Next, the obtained pattern was irradiated with radiation at an exposure amount of 10000 J / m ² using a high-pressure mercury lamp to form a cured film patterned into a predetermined shape.

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 (β-V) was good.

Example 12
[Formation of cured film using curable resin composition (β-VI)]
The curable resin composition (β-VI) prepared in Example 3 was applied on an alkali-free glass substrate with a spinner, and then prebaked on an 80 ° 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 800 J / m ² using a high pressure mercury lamp through a photomask having a predetermined pattern, and a 0.04 mass% potassium hydroxide aqueous solution was used. Development was performed at 23 ° C. for 60 seconds.
Next, the obtained pattern was irradiated with radiation at an exposure amount of 10000 J / m ² using a high-pressure mercury lamp to form a cured film patterned into a predetermined shape.

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 (β-VI) 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 10,000 J / m 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 10,000 J / m ² , and the film thickness before and after the 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 10,000 J / m 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 10 was further subjected to an exposure treatment of 10,000 J / m 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 obtained by the formation method of Example 11 was further subjected to an exposure treatment of 10,000 J / m 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 10,000 J / m 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.

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.

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 38%, 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 34%, 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 30%, 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 43%, 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 47%, 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 45%, and the fluorescence characteristics were judged to be good.

  The cured film formed using the curable resin composition of the present invention is excellent in reliability such as light resistance and is easy to pattern, and as a wavelength conversion layer or wavelength conversion film, a display element or the like is used. In addition to the conventional electronic devices, the present invention can be used in the field of 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 (13)

[A] a polymer having a structural moiety represented by the following formula (1) and a structural moiety represented by the following formula (2);
[B] quantum dots, and
[D] A curable resin composition comprising a polymerizable unsaturated compound.

(In Formula (1), X ¹ represents a hydrogen atom or a monovalent linear or branched saturated hydrocarbon group having 1 to 3 carbon atoms. X ² represents 1 having 3 to 30 carbon atoms. One or more of a valent linear, branched or cyclic saturated or unsaturated hydrocarbon group or a monovalent linear, branched or cyclic saturated or unsaturated hydrocarbon group having 3 to 30 carbon atoms In which a hydrogen atom is substituted with a hydroxy group, a halogen atom, a nitro group, a carboxyl group, an alkyl group which may have a substituent, an aralkyl group, or an alkoxy group.
In formula (2), Y ¹ represents a hydrogen atom or a methyl group. Y ² represents a C 1-12 divalent linear, branched or cyclic saturated or unsaturated hydrocarbon group or a C 1-12 divalent linear, branched or cyclic saturated or A group in which one or more hydrogen atoms of an unsaturated hydrocarbon group are substituted with a hydroxy group, a halogen atom, a nitro group, a carboxyl group, an optionally substituted alkyl group, an aralkyl group, or an alkoxy group . Y ³ represents a divalent organic group. Y ⁴ represents a hydrogen atom. n represents 0 or 1. )   The monomer that gives the structural moiety represented by the formula (2) is 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid The curable resin composition according to claim 1.   [B] The quantum dot is made of a compound containing at least two elements selected from the group consisting of a group 2 element, a group 11 element, a group 12 element, a group 13 element, a group 14 element, a group 15 element, and a group 16 element. The curable resin composition according to claim 1.   [B] The curable resin composition according to claim 1 or 2, wherein the quantum dots are composed of a compound containing In as a constituent component. [B] At least one 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 curable resin composition of any one of Claims 1-3 characterized by the above-mentioned.   Furthermore, [C] a polymerization initiator is contained, The curable resin composition of any one of Claims 1-4 characterized by the above-mentioned. [C] The curable resin composition according to claim 6 , wherein the polymerization initiator is a polymerization initiator having no nitrogen atom in the molecule.   Furthermore, [E] antioxidant is contained, The curable resin composition of any one of Claims 1-7 characterized by the above-mentioned.   [E] The curable resin composition according to claim 8, wherein the antioxidant is a phosphite antioxidant.   A cured film 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 9.   It has a light emitting layer formed using the curable resin composition of any one of Claims 1-9, The light emitting element characterized by the above-mentioned. A method for forming a light emitting layer of a light emitting device, comprising:
(1) The process of forming the coating film of the curable resin composition of any one of Claims 1-9 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 step (2), and (4) a step of exposing the coating film developed in step (3). .