JP6304228B2 - Wavelength conversion film, wavelength conversion substrate, wavelength conversion element and display element - Google Patents

Description

  The present invention relates to a wavelength conversion film, a wavelength conversion substrate, a wavelength conversion element, and a display element.

  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). 1) and as a wavelength conversion material, application to a wavelength conversion element, for example, application to a lighting device or a display element (see Patent Document 2 and Patent Document 3) has been studied. .

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

  In addition, when a semiconductor quantum dot is to be applied to a solar cell panel, a lighting device, a display of a display element, or the like, there is a case where formation of a film composed of semiconductor quantum dots in the form of particles is required in order to use the fluorescence emission . That is, the formation of a wavelength conversion film (wavelength conversion film) that exhibits fluorescence may be required.

  As a method for forming a film using semiconductor quantum dots in the form of particles, for example, as shown in the Examples of Patent Document 1 and Patent Document 2, a method of directly forming a film of semiconductor quantum dots on an appropriate substrate It has been known. However, in such a method, the stability of the formed semiconductor quantum dot film is poor. In particular, there is concern about the binding property between the formed film and the substrate.

  Therefore, a method for forming a film by mixing or embedding semiconductor quantum dots in a particle form in a resin material has been proposed. However, a method for forming a film with a resin using semiconductor quantum dots has not been sufficiently studied. Therefore, for example, there is a demand for a resin material that is used together with semiconductor quantum dots and that is suitable for film formation without reducing the fluorescence emission characteristics of the semiconductor quantum dots.

  In that case, it is particularly desirable that the resin material be used together with a semiconductor quantum dot made of a safe material and be suitable for film formation.

  The present invention has been made in view of the above problems. That is, an object of the present invention is to provide a highly stable wavelength conversion film having excellent fluorescence (wavelength conversion) characteristics including semiconductor quantum dots made of a safe material.

  Another object of the present invention is to provide a highly stable wavelength conversion substrate having a wavelength conversion film having excellent fluorescence (wavelength conversion) characteristics including semiconductor quantum dots made of a safe material.

  Another object of the present invention is to provide a highly stable wavelength conversion element having a wavelength conversion film having excellent fluorescence (wavelength conversion) characteristics including semiconductor quantum dots made of a safe material.

  Moreover, the objective of this invention is providing the display element provided with the highly stable wavelength conversion film comprised including the semiconductor quantum dot which consists of a safe material.

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

  1st aspect of this invention is related with the wavelength conversion film characterized by including a semiconductor quantum dot and resin.

In the first aspect of the present invention, the semiconductor quantum dot comprises:
It is selected from the group consisting of InP / ZnS, CuInS ₂ / ZnS and (ZnS / AgInS ₂ ) solid solution / ZnS that are core-shell structure semiconductor quantum dots, and AgInS ₂ and Zn-doped AgInS ₂ that are homogeneous structure type semiconductor quantum dots At least one is preferred.

  In the first aspect of the present invention, the resin is a cyclic polyolefin resin, an aromatic polyether resin, a polyimide resin, a fluorene polycarbonate resin, a fluorene polyester resin, a polycarbonate resin, a polyamide resin, or a polyarylate resin. , Polysulfone resin, polyethersulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, allyl ester It is preferably at least one selected from the group consisting of a system curable resin and a silsesquioxane ultraviolet curable resin.

  In the first aspect of the present invention, the semiconductor quantum dot is made of a material (A) having a fluorescence maximum in a wavelength region of 500 nm to 600 nm and / or a material (B) having a fluorescence maximum in a wavelength region of 600 nm to 700 nm. Is preferred.

  A second aspect of the present invention relates to a wavelength conversion substrate comprising the wavelength conversion film of the first aspect of the present invention and a base material.

  A 3rd aspect of this invention is related with the wavelength conversion element provided with the wavelength conversion film of the 1st aspect of this invention.

  A 4th aspect of this invention is related with the display element characterized by including the wavelength conversion film of the 1st aspect of this invention.

  According to the first aspect of the present invention, a wavelength conversion film having excellent wavelength conversion characteristics including a quantum dot made of a safe material and having high stability is provided.

  Further, according to the second aspect of the present invention, there is provided a wavelength conversion substrate having a wavelength conversion film having excellent fluorescence (wavelength conversion) characteristics including a semiconductor quantum dot made of a safe material and having high stability. The

  Moreover, according to the 3rd aspect of this invention, the wavelength conversion element provided with the highly stable wavelength conversion film comprised including the quantum dot which consists of a safe material is provided.

  Moreover, according to the 3rd aspect of this invention, the display element provided with the highly stable wavelength conversion film comprised including the quantum dot which consists of a safe material is provided.

It is sectional drawing which shows typically an example of the wavelength conversion board | substrate of embodiment of this invention. It is sectional drawing which shows typically another example of the wavelength conversion film of embodiment of this invention. It is sectional drawing which shows typically the display element of embodiment of this invention. It is sectional drawing which shows typically the structure of the illuminating device of embodiment of this invention.

The wavelength conversion film of the embodiment of the present invention includes a semiconductor quantum dot and a resin. The semiconductor quantum dot contained in the wavelength conversion film of the embodiment of the present invention is a semiconductor quantum dot made of a safe material that does not contain Cd or Pb as a constituent component but contains In (indium) as a constituent component. The resin contained in the wavelength conversion film of the embodiment of the present invention is suitable for constituting a wavelength conversion film that exhibits excellent fluorescence characteristics, that is, excellent wavelength conversion characteristics, using the semiconductor quantum dots. Resin.
Hereinafter, the semiconductor particle dots and the resin contained in the wavelength conversion film of the embodiment of the present invention will be described.

<Semiconductor quantum dots>
The semiconductor quantum dots contained in the wavelength conversion film according to the embodiment of the present invention are composed of elements represented by Group 2 element, Group 11 element, Group 12 element, Group 13 element, Group 14 element, Group 15 element and Group 16 element. A semiconductor quantum dot made of a compound containing at least two elements selected from the group 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 (Sulfur), Se (selenium), Te (tellurium), and a semiconductor quantum dot which consists of a compound containing at least 2 or more types of elements chosen from Po (polonium) group are preferable.

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

  The semiconductor quantum dot is composed of the compound (A) and / or the compound (B) having such a fluorescence emission characteristic, and thereby has a fluorescence maximum in a wavelength region of 500 nm to 600 nm and / or a wavelength region of 600 nm to 700 nm. Can have. As a result, the semiconductor quantum dots can constitute a wavelength conversion film suitable for the structure of a display element that displays an image using light in the visible range.

  Furthermore, the semiconductor quantum dots contained in the wavelength conversion film of the embodiment of the present invention are more preferably semiconductor quantum dots made of a compound containing In as a constituent component. By making the component structure of the semiconductor quantum dot as such, a wavelength conversion film that is safe and has excellent wavelength conversion characteristics can be provided.

  Moreover, the semiconductor quantum dot contained in the wavelength conversion film of the embodiment of the present invention is at least one structural type selected from a homogeneous structural type composed of one compound and a core-shell structural type composed of two or more compounds. The semiconductor quantum dot is preferably used.

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

The semiconductor quantum dots contained in the wavelength conversion film of the embodiment of the present invention are InP / ZnS, CuInS ₂ / ZnS, and (ZnS / AgInS ₂ ), which are core-shell structure type semiconductor quantum dots, in consideration of the component configuration and structure. It is preferably at least one selected from the group consisting of solid solution / ZnS and homogeneous structure type semiconductor quantum dots AgInS ₂ and Zn-doped AgInS ₂ .
When the semiconductor quantum dot has such a configuration, it is possible to provide a stable wavelength conversion film that is safe and has more excellent wavelength conversion characteristics.

  Moreover, as for the semiconductor quantum dot contained in the wavelength conversion film of embodiment of this invention, it is desirable that an average particle diameter is about 1.0 nm-10 nm. When the average particle size is less than about 1.0 nm, it is difficult to prepare a semiconductor quantum dot, and even if the semiconductor quantum dot can be prepared, the semiconductor quantum dot may be in an unstable state. When the average particle diameter exceeds 10 nm, the quantum confinement effect due to the size of the semiconductor quantum dots may not be obtained, which is not desirable.

  As a method for obtaining the semiconductor quantum dots contained in the wavelength conversion film of the embodiment of the present invention, a known method for thermally decomposing an organometallic compound in a coordinating organic solvent can be used. For core-shell structure type semiconductor quantum dots, after forming a homogeneous core structure by reaction, a precursor for forming a shell on the core surface is added to the reaction system, and the reaction is stopped after the shell formation. And can be obtained by separating from the solvent. A commercially available product can also be used.

<Resin>
Although the wavelength conversion film of embodiment of this invention will not be restrict | limited especially if the above-mentioned semiconductor quantum dot and resin are contained, As that resin, transparent resin is preferable. Such a resin is not particularly limited as long as it does not impair the effect of the wavelength conversion film of the present invention. For example, it ensures thermal stability and moldability to a film, and is applied to display elements and the like. The glass transition temperature (Tg) is preferably 110 ° C. to 380 ° C., more preferably 110 ° C. to 370 ° C., and further preferably 120 ° C. to 360 ° C. The resin which is is mentioned.

  Moreover, as said resin, the total light transmittance (JIS K7105) in thickness 0.1mm becomes like this. Preferably it is 75%-95%, More preferably, it is 78%-95%, More preferably, it is 80 % -95% resin can be used. When the total light transmittance is in such a range, the obtained wavelength conversion film exhibits good transparency as an optical film.

  Also, a resin that is used together with semiconductor quantum dots and is suitable for film formation without reducing the fluorescence emission characteristics of the semiconductor quantum dots is preferable.

In that case, in particular, semiconductor quantum dots made of a safe material, particularly InP / ZnS, CuInS ₂ / ZnS and (ZnS / AgInS ₂ ) solid solution / ZnS, which are core-shell structure type semiconductor quantum dots, and homogeneous structure type semiconductor quantum A resin material that is used together with at least one selected from the group consisting of dots of AgInS ₂ and Zn-doped AgInS ₂ and is suitable for forming a film including the semiconductor quantum dots is desirable.

  Examples of the resin as described above include cyclic polyolefin resins, aromatic polyether resins, polyimide resins, fluorene polycarbonate resins, fluorene polyester resins, polycarbonate resins, polyamide (aramid) resins, and polyarylate resins. Resins, polysulfone resins, polyethersulfone resins, polyparaphenylene resins, polyamideimide resins, polyethylene naphthalate (PEN) resins, fluorinated aromatic polymer resins, (modified) acrylic resins, epoxy resins Examples thereof include resins, allyl ester curable resins, and silsesquioxane ultraviolet curable resins.

  Hereinafter, particularly preferred resins will be described in more detail with respect to the resins listed as preferred for forming the wavelength conversion film of the embodiment of the present invention.

(1) Cyclic olefin resin The cyclic olefin resin described above is at least selected from the group consisting of a monomer represented by the following formula (X ₀ ) and a monomer represented by the following formula (Y ₀ ). A resin obtained from one monomer or a resin obtained by hydrogenating the resin as required is preferred.

In the formula _{^{(X 0), R x1 ~R}} x4 each independently represent the following (i ') ~ (viii' ) than chosen atom or ^group, k x, ^{m x} and ^{p x} are each independently Represents 0 or a positive integer.
(I ′) a hydrogen atom (ii ′) a halogen atom (iii ′) a trialkylsilyl group (iv ′) a substituted or unsubstituted carbon atom having a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom -30 hydrocarbon group (v ') substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms (vi') polar group (excluding (iv '))
(Vii ′) R ^x1 and R ^x2 or R ^x3 and R ^x4 represent an alkylidene group formed by bonding to each other, and R ^{x1 to} R ^x4 not participating in the bonding are each independently the above (i Represents an atom or group selected from ') to (vi').
(Viii ′) R ^x1 and R ^x2 or R ^x3 and R ^x4 represent a monocyclic or polycyclic hydrocarbon ring or heterocyclic ring formed by bonding to each other, and R ^{x1 to} R not participating in the bonding ^x4 each independently represents an atom or group selected from the above (i ′) to (vi ′), or a monocyclic hydrocarbon ring formed by bonding R ^x2 and R ^x3 to each other; R ^{x1 to} R ^x4 representing a heterocyclic ring and not involved in the bond each independently represent an atom or group selected from the above (i ′) to (vi ′).

In the above formula (Y ₀ ), R ^y1 and R ^y2 each independently represent an atom or group selected from the above (i ′) to (vi ′), or the following (ix ′), and k ^y and p ^y independently represents 0 or a positive integer.
(Ix ′) R ^y1 and R ^{y2 represent} a monocyclic or polycyclic alicyclic hydrocarbon, aromatic hydrocarbon or heterocyclic ring formed by bonding to each other.

(2) Aromatic polyether-based resin The aromatic polyether-based resin described above is at least one selected from the group consisting of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2). It preferably has one structural unit.

The formula ^(1), R 1 to R ⁴ are each independently a monovalent organic group having 1 to 12 carbon atoms, to d represents an integer of 0 to 4 independently.

In the above formula ^(2), R 1 to R ⁴ and a~d are the same as ^R 1 to R ⁴ and a~d each independently the above formula (1), Y represents a single bond, -SO ₂ -Or> C = O, R ⁷ and R ⁸ each independently represent a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group, and g and h each independently represent 0 to 4 And m represents 0 or 1.
However, when m is 0, R ⁷ is not a cyano group.

  The aromatic polyether-based resin described above further has at least one structural unit selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4). Is preferred.

In the above formula (3), R ⁵ and R ⁶ each independently represent a monovalent organic group having 1 to 12 carbon atoms, and Z represents a single bond, —O—, —S—, —SO ₂ —, > C═O, —CONH—, —COO— or a divalent organic group having 1 to 12 carbon atoms, e and f each independently represent an integer of 0 to 4, and n represents 0 or 1 .

In the above formula (4), R ⁷ , R ⁸ , Y, m, g and h are each independently synonymous with R ⁷ , R ⁸ , Y, m, g and h in the above formula (2), R ^{5, R} 6, Z, n, e and f have the same meanings as respectively ^{R 5,} R 6, Z independently in the above formula (3) in, n, e and f.

(3) Polyimide-based resin The polyimide-based resin described above is not particularly limited, and may be any polymer compound including an imide bond in a repeating unit. For example, JP-A-2006-199945 and JP-A-2008-163107. It can be synthesized by the method described in the publication.

(4) Fluorene polycarbonate-based resin The fluorene polycarbonate-based resin is not particularly limited, and may be any polycarbonate resin including a fluorene moiety. For example, the fluorene polycarbonate-based resin is synthesized by a method described in Japanese Patent Application Laid-Open No. 2008-163194. be able to.

(5) Fluorene polyester-based resin The fluorene polyester-based resin is not particularly limited as long as it is a polyester resin containing a fluorene moiety. For example, in JP 2010-285505 A and JP 2011-197450 A It can be synthesized by the method described.

(6) Fluorinated aromatic polymer-based resin The above-mentioned fluorinated aromatic polymer-based resin is not particularly limited, but includes an aromatic ring having at least one fluorine, an ether bond, a ketone bond, a sulfone bond, an amide bond, Any polymer containing a repeating unit containing at least one bond selected from the group consisting of an imide bond and an ester bond may be used. For example, the polymer can be synthesized by the method described in JP-A-2008-181121. .

(7) Commercial product The resin mentioned as preferable for the configuration of the wavelength conversion film of the embodiment of the present invention can be obtained by purchase.
Examples of commercially available resins preferable for the configuration of the wavelength conversion film of the embodiment of the present invention include the following commercially available products. Examples of commercially available products of cyclic olefin resins include Arton (registered trademark) manufactured by JSR Corporation, ZEONOR (registered trademark) manufactured by ZEON CORPORATION, APEL (registered trademark) manufactured by Mitsui Chemicals, Inc., and manufactured by Polyplastics Corporation. And TOPAS (registered trademark). Examples of commercially available polyethersulfone resins include Sumika Excel (registered trademark) PES manufactured by Sumitomo Chemical Co., Ltd. Examples of commercially available polyimide resins include Neoprim (registered trademark) L manufactured by Mitsubishi Gas Chemical Company, Inc. Examples of commercially available polycarbonate resins include Pure Ace (registered trademark) manufactured by Teijin Limited. As a commercial item of a fluorene polycarbonate-type resin, Mitsubishi Gas Chemical Co., Ltd. Iupizeta (trademark) EP-5000 etc. can be mentioned, for example. Examples of commercially available fluorene polyester resins include OKP4HT manufactured by Osaka Gas Chemical Co., Ltd. As a commercial item of acrylic resin, for example, Nippon Catalyst Co., Ltd. AKRIVIEWER (registered trademark) can be cited. Examples of commercially available silsesquioxane-based UV curable resins include Silplus (registered trademark) manufactured by Nippon Steel Chemical Co., Ltd.

<Method for producing wavelength conversion film>
The wavelength conversion film of the embodiment of the present invention includes a semiconductor quantum dot and a resin, and the content of the semiconductor quantum dot is preferably 0. The amount is from 01 to 100 parts by weight, more preferably from 0.02 to 50 parts by weight, particularly preferably from 0.03 to 30 parts by weight. When the content of the semiconductor quantum dots is within the above range, a wavelength conversion film having excellent wavelength conversion characteristics can be provided.

The wavelength conversion film according to the embodiment of the present invention can be formed by, for example, melt molding or cast molding, and if necessary, a coating agent such as an antireflection agent, a hard coating agent and / or an antistatic agent after molding. Can be produced by a coating method.
Below, the manufacturing method of a wavelength conversion film is demonstrated.

(1) Melt molding A wavelength conversion film according to an embodiment of the present invention is a method for melt-molding pellets obtained by melt-kneading a resin and semiconductor quantum dots, and a resin composition containing the resin and semiconductor quantum dots. Can be produced by a melt molding method, a pellet obtained by removing a solvent from a resin composition containing semiconductor quantum dots, a resin and a solvent, or the like. Examples of the melt molding method include injection molding, melt extrusion molding, and blow molding.

(2) Cast molding A wavelength conversion film according to an embodiment of the present invention is a method of removing a solvent by casting a resin composition containing semiconductor quantum dots, a resin and a solvent on a suitable base material; A method of casting a resin composition comprising a coating agent such as a coating agent and an antistatic agent, a semiconductor quantum dot, and a resin on an appropriate substrate; or an antireflection agent, a hard coating agent and / or a charge It can also be produced by a method in which a curable composition containing a coating agent such as an inhibitor, a semiconductor quantum dot, and a resin is cast on a suitable substrate and cured and dried.

  Examples of the substrate include a glass plate, a steel belt, a steel drum, and a transparent resin (for example, a polyester film and a cyclic olefin resin film).

  The wavelength conversion film of the above-described embodiment of the present invention can be obtained by peeling from the substrate, and unless the effect of the present invention is impaired, the substrate and the coating film are not peeled off from the substrate. It is good also as a wavelength conversion board | substrate provided with the wavelength conversion film of embodiment of this invention for a laminated body.

  Moreover, the wavelength conversion film of embodiment of this invention can also be used as a patterned layer or film | membrane like the color filter of the flat panel display using a liquid crystal etc., for example. In that case, a resin composition containing semiconductor quantum dots, a resin, and a solvent is formed as a layer or film that has been subjected to desired patterning by an appropriate printing method such as screen printing on an appropriate substrate for a display element. Thereafter, the solvent is removed, and the wavelength conversion film of the embodiment of the present invention can be formed as a patterned wavelength conversion film.

  Further, by a method of coating the above resin composition on an optical component such as a glass plate, quartz or transparent plastic and drying the solvent, or a method of coating and curing and drying the above curable composition A resin substrate can also be formed directly on the optical component.

  The amount of residual solvent in the wavelength conversion film obtained by the above method should be as small as possible. Specifically, the amount of the residual solvent is preferably 3% by weight or less, more preferably 1% by weight or less, and still more preferably 0.5% by weight or less based on the weight of the film. When the amount of residual solvent is in the above-mentioned range, a wavelength conversion film that can easily exhibit a desired function is obtained, in which deformation and characteristics hardly change.

<Wavelength conversion film, wavelength conversion substrate and display element>
FIG. 1 is a cross-sectional view schematically showing an example of a wavelength conversion substrate according to an embodiment of the present invention.

  As shown in FIG. 1, a wavelength conversion substrate 1 that is an example of an embodiment of the present invention includes a base material 2 and a wavelength conversion film 3 disposed on the base material 2.

  The wavelength conversion film 3 of the wavelength conversion substrate 1 includes the semiconductor quantum dots and the resin described above. The substrate 2 is made of glass, quartz, or transparent resin (for example, transparent polyimide, polyethylene naphthalate, polyethylene terephthalate, polyester film, cyclic olefin resin film, etc.).

  In the wavelength conversion substrate 1, the wavelength conversion film 3 converts the wavelength of the excitation light from the excitation light source using semiconductor quantum dots and converts it into light having a desired wavelength. Therefore, the wavelength conversion board | substrate 1 becomes a suitable thing as an energy conversion board | substrate for solar cells. In addition, a wavelength conversion element can be provided in combination with an appropriate excitation light source, and is suitable for, for example, a configuration of a lighting device or a display element.

  For example, when a color display is to be formed by providing one on the entire surface of a display element capable of full dot display, the wavelength conversion substrate 1 is provided on the opposite side of the wavelength conversion substrate in order to extract RGB light. It is preferable to use a color filter. As the color filter, those produced by a known method can be suitably used.

  When used for a display element, the film thickness of the wavelength conversion film is preferably about 100 nm to 100 μm, and more preferably 1 μm to 100 μm. When the film thickness is less than 100 nm, excitation light cannot be sufficiently absorbed, and the light conversion efficiency is lowered, so that there is a problem that sufficient brightness of the panel cannot be secured. Furthermore, the film thickness is preferably 1 μm or more in order to enhance absorption of excitation light and sufficiently ensure the brightness of the panel.

  When the wavelength conversion substrate of the embodiment of the present invention is used for the configuration of a display element, for example, a light-emitting display element can be configured by combining with a light-emitting element such as an organic EL element as an excitation light source.

  In that case, the wavelength conversion substrate of the present embodiment provided with the wavelength conversion film of the present embodiment emits, for example, red light, green light, and blue light independently as in the case of a color filter in a conventional liquid crystal display element or the like. It is preferable to have the function of

  That is, in a conventional full color liquid crystal display element using a color filter, an image is formed by three types of subpixels: a subpixel that performs red display, a subpixel that performs green display, and a subpixel that performs blue display. One pixel which is the minimum unit constituting the. Then, the color filter is configured so that the red coloring layer, the green coloring layer, and the blue coloring layer correspond to the sub pixel that performs red display, the sub pixel that performs green display, and the sub pixel that performs blue display, respectively. Patterned and arranged. For example, a black matrix for preventing color mixing or the like is provided between the three types of sub-pixels.

  Therefore, it is preferable that the wavelength conversion substrate of the present embodiment using the wavelength conversion film of the present embodiment is also configured to enable full color display on the display element. That is, the wavelength conversion film that emits light of each color of red, green, and blue is patterned so as to correspond to the sub-pixel that displays red, the sub-pixel that displays green, and the sub-pixel that displays blue. It is preferable to provide it.

  FIG. 2 is a cross-sectional view schematically showing another example of the wavelength conversion film of the embodiment of the present invention.

  As shown in FIG. 2, another example of the wavelength conversion substrate 11 according to the embodiment of the present invention includes a base material 12 and wavelength conversion films 13 a, 13 b, and 13 c disposed on the base material 12. A black matrix 14 is disposed between the wavelength conversion films 13a, 13b, and 13c. 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.

  In the wavelength conversion substrate 11, a wavelength conversion film 13a that converts excitation light into red light, a wavelength conversion film 13b that converts excitation light into green light, and a wavelength conversion film 13c that converts excitation light into blue light Are respectively patterned and arranged.

  The film thickness of the wavelength conversion films 13a, 13b, and 13c is preferably about 100 nm to 100 μm, and more preferably 1 μm to 100 μm. When the film thickness is less than 100 nm, the excitation light cannot be sufficiently absorbed, and there is a risk that luminance is insufficient due to a decrease in light conversion efficiency. In particular, when visible light such as blue light is used as excitation light, there arises a problem of deterioration in color purity due to mixing of the transmitted light of excitation light with a required color in addition to a decrease in light conversion efficiency. In order to increase the absorption of the excitation light and reduce the transmitted light of the excitation light to such an extent that the color purity is not adversely affected, the film thickness is preferably 1 μm or more.

  The black matrix 14 provided between the three types of wavelength conversion films 13a to 13c is provided, for example, so as to suppress color mixing of colored light emitted from the wavelength conversion films 13a to 13c.

  The wavelength conversion substrate 11 can be used together with a light emitting element (not shown) serving as an excitation light source to constitute a light emitting display element. In this case, the wavelength conversion films 13a to 13c are provided corresponding to the sub-pixel that performs red display, the sub-pixel that performs green display, and the sub-pixel that performs blue display, respectively, and can display full color on the display element. And

  FIG. 3 is a cross-sectional view schematically showing the display element of the embodiment of the present invention.

  The display element 100 of this embodiment is configured using the wavelength conversion substrate 11 of this embodiment described above. Therefore, the same components as those of the wavelength conversion substrate 11 in FIG. 2 are denoted by the same reference numerals, and redundant description is omitted.

  The display element 100 of this embodiment includes a wavelength conversion substrate 11 configured by providing wavelength conversion films 13 a, 13 b, 13 c and a black matrix 14 on a base material 12, and an adhesive layer 15 on the wavelength conversion substrate 11. And a light source substrate 18 bonded to each other. 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. 3, the adhesive layer 15 does not need to be provided on the base 12 so as to cover the entire surface of the wavelength conversion films 13 a, 13 b, and 13 c, and is provided only around the wavelength conversion substrate 11. Is also possible.

  The light source substrate 18 includes a base material 16 and light sources 17a, 17b, and 17c disposed on the wavelength conversion substrate 11 side of the base material 16. Each of the light sources 17a, 17b, and 17c emits ultraviolet light or blue light as excitation light.

  As the light sources 17a, 17b, and 17c, ultraviolet light emitting organic EL elements and blue light emitting organic EL elements having a known structure can be used, and are not particularly limited, and are manufactured using known materials and known manufacturing methods. Is possible. 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. It is desirable that the light sources 17a, 17b, and 17c have directivity so as to irradiate the wavelength conversion films 13a, 13b, and 13c opposed to the respective emitted lights.

  The display element 100 of the present embodiment converts the wavelength of the excitation light from the light sources 17a, 17b, and 17c by the semiconductor quantum dots of the wavelength conversion films 13a, 13b, and 13c of the wavelength conversion substrate 11, and displays visible light having a desired wavelength. Used for display.

  As described above, the wavelength conversion substrate 11 of the display element 100 is formed by patterning the wavelength conversion films 13 a, 13 b, and 13 c using semiconductor quantum dots and resin on the base material 12.

  In addition, in the wavelength conversion board | substrate 11, excitation light is converted into blue light in the wavelength conversion film 13c so that it may mention later. At this time, instead of the wavelength conversion film 13c, the wavelength conversion substrate 11 can use a light scattering film configured by dispersing photoacid scattering particles in the same resin as that used by the wavelength conversion film 13c. It is. By doing so, when the excitation light is blue light, the excitation light can be used as it is without converting the wavelength.

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

  And the display element 100 comprises one pixel which is the minimum unit which comprises an image by three types of subpixels provided with wavelength conversion film 13a, 13b, 13c.

  In the display element 100 of the present embodiment having the above-described configuration, the emission of light of three types of red, green, and blue is controlled for each of the three types of subpixels including the wavelength conversion films 13a, 13b, and 13c. Full color display is performed.

  In the display element according to the embodiment of the present invention, a color filter can be provided between the wavelength conversion films 13 a, 13 b, 13 c and the substrate 12. That is, a red color filter is provided between the wavelength conversion film 13a and the substrate 12, a green color filter is provided between the wavelength conversion film 13b and the substrate 12, and the wavelength conversion film 13c and the substrate 12 A red color filter can be provided therebetween.

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

<Lighting device>
The wavelength conversion film of embodiment of this invention can be used for the structure of a wavelength conversion element, for example, as mentioned above, can provide a display element. As another wavelength conversion element, for example, an illumination device can be provided in combination with an appropriate excitation light source.

  FIG. 4 is a cross-sectional view schematically showing the configuration of the illumination device according to the embodiment of the present invention.

  As shown in FIG. 4, the illumination device 200 according to the embodiment of the present invention includes a light source 101 and a wavelength conversion film 102. And it can have the holding body 103 for hold | maintaining them and guide | inducing the light from the light source 101 to the wavelength conversion film 102 efficiently. In addition, when necessary, it can have a diffusion plate 104 for diffusing light emitted from the wavelength conversion film 102 in various directions.

In the example shown in FIG. 4, the wavelength conversion film 102 can be provided on a base material (not shown) and held by the holding body 103 together with the base material.
In FIG. 4, the wavelength conversion film 102 is disposed so as to be separated from the light source 101, but can be disposed directly on the light source 101 or on the light source 101 via an appropriate base material. is there.

  As the light source 101, for example, a blue LED (Light Emitting Diode) that emits blue light, an ultraviolet light-emitting LED that emits ultraviolet light, or the like can be used.

  In the illumination device 200, the wavelength conversion film 102 includes the semiconductor quantum dots and the resin described above. The wavelength conversion film 102 converts the wavelength of excitation light from the light source 101 using semiconductor quantum dots, converts the light into light having a desired wavelength, and then emits the light to the diffusion plate 104 side.

  For example, when the light source 101 is a blue LED, the wavelength conversion film 102 is preferably configured to include semiconductor quantum dots that convert blue light from the light source 101 into yellow light. In that case, the wavelength conversion film 102 can convert a part of the blue light from the light source 101 into yellow light corresponding to the complementary color, and emit it as white light added together. And the illuminating device 200 can diffuse the white light inject | emitted from the wavelength conversion film 102 with the diffuser plate 104, and can utilize it as illumination light.

  As a result, the lighting device 200 can extract light from the light source 101 as white light using the wavelength conversion film 102, and can be used as a lighting device for white light emission.

  In addition, in the above-mentioned example, as a semiconductor quantum dot contained in the wavelength conversion film 102, what converts blue light into yellow light, and what converts red light and blue-green light can also be used. By using such a plurality of types of semiconductor quantum dots, the color rendering property of white light extracted using the wavelength conversion film 102 can be improved.

  When the light source 101 is an ultraviolet light emitting LED, the wavelength conversion film 102 converts the semiconductor quantum dot that converts ultraviolet light from the light source 101 into red light, the semiconductor quantum dot that converts green light, and blue light. It is preferable that it is comprised including the semiconductor quantum dot to perform.

  As a result, the lighting device 200 can extract light from the light source 101 as white light with excellent color rendering properties using the wavelength conversion film 102, and can be used as a lighting device for white light emission with high color rendering properties. .

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to these Examples at all. In the description, “parts” means “parts by weight” unless otherwise specified. Moreover, the measuring method of each physical property value is as follows.

<Molecular weight>
The molecular weight of the resin was measured by the following method (a) or (b) in consideration of the solubility of each resin in a solvent.
(A) Weight average molecular weight in terms of standard polystyrene using a gel permeation chromatography (GPC) apparatus (150C type, column: H type column manufactured by Tosoh Corporation, developing solvent: o-dichlorobenzene) manufactured by WATERS (Mw) and number average molecular weight (Mn) were measured.
(B) The weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of standard polystyrene were measured using a GPC apparatus (HLC-8220 type, column: TSKgel α-M, developing solvent: THF) manufactured by Tosoh Corporation.

In addition, about the resin synthesize | combined in the resin synthesis example 3 mentioned later, the logarithmic viscosity was measured by the following method (c) instead of the molecular weight measurement by the said method.
(C) A part of the polyimide resin solution was added to anhydrous methanol to precipitate the polyimide resin, and filtered to separate from the unreacted monomer. 0.1 g of polyimide obtained by vacuum drying at 80 ° C. for 12 hours is dissolved in 20 mL of N-methyl-2-pyrrolidone, and the logarithmic viscosity (μ) at 30 ° C. is obtained by the following formula using a Canon-Fenske viscometer. Asked.

t ₀ : Flowing time of solvent t _s : Flowing time of dilute polymer solution C: 0.5 g / dL

<Glass transition temperature (Tg)>
Using a differential scanning calorimeter (DSC6200) manufactured by SII Nano Technologies, Inc., the rate of temperature increase was measured at 20 ° C. per minute under a nitrogen stream.

<Semiconductor quantum dots>
The semiconductor quantum dots used in this example and their fluorescence maximum wavelengths are shown below.
Semiconductor quantum dot A: InP / ZnS core-shell quantum dot (fluorescence maximum wavelength: 630 nm)
Semiconductor quantum dot B: InCuS ₂ / ZnS core-shell type quantum dot (fluorescence maximum wavelength: 640 nm)
Semiconductor quantum dot C: AgInS ₂ quantum dot (fluorescence maximum wavelength: 650 nm)
Semiconductor quantum dot D: ZnS-AgInS ₂ solid solution / ZnS core-shell quantum dot (fluorescence maximum wavelength: 640 nm)
Semiconductor quantum dot E: Zn-doped AgInS ₂ quantum dot (fluorescence maximum wavelength: 630 nm)

Then, semiconductor quantum dots A: InP / ZnS core-shell quantum dots, semiconductor quantum dots B: InCuS ₂ / ZnS core-shell quantum dots, semiconductor quantum dots C: AgInS ₂ quantum dots, semiconductor quantum dots D: ZnS-AgInS ₂ solid solution / ZnS core-shell quantum dots and semiconductor quantum dots E: Zn-doped AgInS ₂ quantum dots can be synthesized by a generally known method.

For example, regarding the semiconductor quantum dot A: InP / ZnS core-shell type quantum dot, the technical literature “Journal of American Chemical Society. 2007, 129, 15432-15433” and the semiconductor quantum dot B: InCuS ₂ / ZnS core-shell type quantum dot In the technical document “Journal of American Chemical Society. 2009, 131, 5691-5697” and the technical document “Chemistry of Materials. 2009, 21, 2422-2429”, the semiconductor quantum dot C: AgInS ₂ quantum ur of American Chemical Society. 2009, 131, 5691-5697 " , Semiconductor quantum dots D: technical literature with respect to ZnS-AgInS ₂ solid solution / ZnS core-shell quantum dots "Chemical Communications 2010, 46, 2082-2084.", The semiconductor quantum dot E: technical literature with respect to Zn-doped AgInS ₂ quantum dots It can be synthesized with reference to the method described in “Journal of Physical Chemistry C. 2012, 116, 9769-9773”.

<Resin synthesis example 1>
8-methyl-8-methoxycarbonyltetracyclo represented by the following formula (a) [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca-3-ene (hereinafter also referred to as “DNM”) 100 parts, 1-hexene (molecular weight regulator) 18 parts and toluene (ring-opening polymerization solvent) 300 parts nitrogen-substituted reaction The vessel was charged and the solution was heated to 80 ° C. Next, 0.2 parts of a toluene solution of triethylaluminum (0.6 mol / liter) as a polymerization catalyst and a toluene solution of methanol-modified tungsten hexachloride (concentration 0.025 mol / liter) were added to the solution in the reaction vessel. 9 parts was added and this solution was heated and stirred at 80 ° C. for 3 hours to cause a ring-opening polymerization reaction to obtain a ring-opening polymer solution. The polymerization conversion rate in this polymerization reaction was 97%.

1000 parts of the ring-opening polymer solution thus obtained was charged into an autoclave, and 0.12 part of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opening polymer solution. Under the conditions of a hydrogen gas pressure of 100 kg / cm ² and a reaction temperature of 165 ° C., the hydrogenation reaction was performed by heating and stirring for 3 hours.

  After cooling the obtained reaction solution (hydrogenated polymer solution), the hydrogen gas was released. This reaction solution was poured into a large amount of methanol to separate and recover a coagulated product, which was dried to obtain a hydrogenated polymer (hereinafter also referred to as “resin A”). The obtained resin A had a number average molecular weight (Mn) of 32000, a weight average molecular weight (Mw) of 137,000, and a glass transition temperature (Tg) of 165 ° C.

<Resin synthesis example 2>
In a 3 L four-necked flask, 35.12 g (0.253 mol) of 2,6-difluorobenzonitrile, 87.60 g (0.250 mol) of 9,9-bis (4-hydroxyphenyl) fluorene, 41. 46 g (0.300 mol), 443 g of N, N-dimethylacetamide (hereinafter also referred to as “DMAc”) and 111 g of toluene were added. Subsequently, a thermometer, a stirrer, a three-way cock with a nitrogen introduction tube, a Dean-Stark tube and a cooling tube were attached to the four-necked flask.

  Next, after the atmosphere in the flask was replaced with nitrogen, the resulting solution was reacted at 140 ° C. for 3 hours, and water produced was removed from the Dean-Stark tube as needed. When no more water was observed, the temperature was gradually raised to 160 ° C. and reacted at that temperature for 6 hours.

  After cooling to room temperature (25 ° C.), the produced salt was removed with a filter paper, the filtrate was poured into methanol for reprecipitation, and the filtrate (residue) was isolated by filtration. The obtained filtrate was vacuum dried at 60 ° C. overnight to obtain a white powder (hereinafter also referred to as “resin B”) (yield 95%). The obtained resin B had a number average molecular weight (Mn) of 75000, a weight average molecular weight (Mw) of 188000, and a glass transition temperature (Tg) of 285 ° C.

<Resin synthesis example 3>
In a 500 mL five-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube, a dropping funnel with a side tube, a Dean-Stark tube and a cooling tube, 1,4-bis (4-amino-α, α -Dimethylbenzyl) benzene (27.66 g, 0.08 mol) and 4,4'-bis (4-aminophenoxy) biphenyl (7.38 g, 0.02 mol) were added, and γ-butyrolactone (68.65 g) and N, It was dissolved in 17.16 g of N-dimethylacetamide. The resulting solution was cooled to 5 ° C. using an ice-water bath, and while maintaining the same temperature, 22.62 g (0.1 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and an imidization catalyst As a result, 0.50 g (0.005 mol) of triethylamine was added all at once. After completion of the addition, the temperature was raised to 180 ° C. and refluxed for 6 hours while distilling off the distillate as needed. After completion of the reaction, the reaction mixture was air-cooled until the internal temperature reached 100 ° C., diluted by adding 143.6 g of N, N-dimethylacetamide, cooled with stirring, and 264.16 g of a polyimide resin solution having a solid content concentration of 20% by weight. Got. A part of this polyimide resin solution was poured into 1 L of methanol to precipitate the polyimide. The polyimide separated by filtration was washed with methanol and then dried in a vacuum dryer at 100 ° C. for 24 hours to obtain a white powder (hereinafter also referred to as “resin C”). The IR spectrum of the obtained resin C was measured, ^{1704 cm} -1 characteristic of imido group, absorption of 1770 cm ^-1 were observed. Resin C had a glass transition temperature (Tg) of 310 ° C. and a logarithmic viscosity of 0.87.

<Resin synthesis example 4>
9.167 kg (20.90 mol) of 9,9-bis {4- (2-hydroxyethoxy) phenyl} fluorene, 4.585 kg (20.08 mol) of bisphenol A, 9.000 kg (42.01 mol) of diphenyl carbonate , And 0.02066 kg (2.459 × 10 ⁻⁴ mol) of sodium bicarbonate were placed in a 50 L reactor equipped with a stirrer and a distillation apparatus, and heated to 215 ° C. over 1 hour under a nitrogen atmosphere at 760 Torr. Stir. Thereafter, the degree of vacuum was adjusted to 150 Torr over 15 minutes, and the mixture was held at 215 ° C. and 150 Torr for 20 minutes to conduct a transesterification reaction. Further, the temperature was raised to 240 ° C. at a rate of 37.5 ° C./Hr, and held at 240 ° C. and 150 Torr for 10 minutes. Thereafter, the pressure was adjusted to 100 Torr over 10 minutes and maintained at 240 ° C. and 120 Torr for 70 minutes. Thereafter, the pressure was adjusted to 100 Torr over 10 minutes and held at 240 ° C. and 100 Torr for 10 minutes. The polymerization reaction was further carried out by stirring for 10 minutes under the conditions of 240 ° C. and 1 Torr or less, at 40 ° C. for 1 Torr or less. After completion of the reaction, nitrogen was introduced into the reactor to increase the pressure, and the produced polycarbonate resin (hereinafter also referred to as “resin D”) was extracted while being pelletized. The obtained resin D had a weight average molecular weight of 41,000 and a glass transition temperature (Tg) of 152 ° C.

<Resin synthesis example 5>
To the reactor, 0.8 mol of 9,9-bis {4- (2-hydroxyethoxy) -3,5-dimethylphenyl} fluorene, 2.2 mol of ethylene glycol and 1.0 mol of dimethyl isophthalate were added and stirred. The mixture was gradually heated and melted to carry out a transesterification reaction, and then 20 × 10 ⁻⁴ moles of germanium oxide was added, and ethylene glycol was removed while gradually increasing the temperature and reducing the pressure until reaching 290 ° C. and 1 Torr or less. . Thereafter, the contents were taken out of the reactor to obtain pellets of polyester resin (hereinafter also referred to as “resin E”). The obtained resin E had a number average molecular weight of 40000 and a glass transition temperature of 145 ° C.

<Resin synthesis example 6>
To a reactor equipped with a thermometer, a cooling pipe, a gas introduction pipe and a stirrer, 4,74′-bis (2,3,4,5,6-pentafluorobenzoyl) diphenyl ether (BPDE) 16.74 parts, 10.5 parts of 9-bis (4-hydroxyphenyl) fluorene (HF), 4.34 parts of potassium carbonate and 90 parts of DMAc were charged. The mixture was warmed to 80 ° C. and reacted for 8 hours. After completion of the reaction, the reaction solution was added into a 1% aqueous acetic acid solution with vigorous stirring with a blender. The precipitated reaction product was separated by filtration, washed with distilled water and methanol, and then dried under reduced pressure to obtain a fluorinated polyether ketone (hereinafter also referred to as “resin F”). The obtained resin F had a number average molecular weight of 71,000 and a glass transition temperature (Tg) of 242 ° C.

[Example 1]
By adding 100 parts by weight of the resin A obtained in Synthesis Example 1, 10 parts by weight of semiconductor quantum dots A (fluorescence maximum wavelength: 630 nm), and further adding methylene chloride to the container, a resin solution having a resin concentration of 20% by weight was obtained. . Next, the obtained semiconductor quantum dot A-containing resin solution was cast on a smooth glass plate, dried at 20 ° C. for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried at 100 ° C. under reduced pressure for 8 hours to obtain a wavelength conversion film having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm.

  When blue light having a peak wavelength of 450 nm was irradiated as excitation light to the obtained wavelength conversion film using a blue LED, the wavelength of the excitation light was converted in the wavelength conversion film, and red light was emitted from the wavelength conversion film. I was sure that.

[Example 2] to [Example 11]
A wavelength conversion film having a thickness of 0.105 mm was produced in the same manner as in Example 1 except that the resin, solvent, and film drying conditions shown in Table 1 were employed. The production conditions of the wavelength conversion film are shown in Table 1. In Table 1, the number of added parts of the resin is 100 parts by weight, and the concentration of the resin solution is 20% by weight. Moreover, resin other than resin AF used in Example 1-Example 55, a solvent, and film drying conditions are as having shown below.

[Example 12] to [Example 22]
A semiconductor quantum dot B (fluorescence maximum wavelength: 640 nm) was used as the semiconductor quantum dot, and the thickness of 0.105 mm was the same as in Example 1 except that the resin, solvent, and film drying conditions shown in Table 1 were employed. A wavelength conversion film was produced. The production conditions of the wavelength conversion film are shown in Table 1.

[Example 23] to [Example 33]
A semiconductor quantum dot C (fluorescence maximum wavelength: 650 nm) was used as the semiconductor quantum dot, and the thickness of 0.105 mm was the same as in Example 1 except that the resin, solvent, and film drying conditions shown in Table 1 were employed. A wavelength conversion film was produced. The production conditions of the wavelength conversion film are shown in Table 1.

[Example 34] to [Example 44]
A semiconductor quantum dot D (fluorescence maximum wavelength: 640 nm) was used as the semiconductor quantum dot, and the thickness of 0.105 mm was the same as in Example 1 except that the resin, solvent, and film drying conditions shown in Table 2 were employed. A wavelength conversion film was produced. Table 2 shows the production conditions of the wavelength conversion film.

[Example 45] to [Example 55]
A semiconductor quantum dot E (fluorescence maximum wavelength: 630 nm) was used as the semiconductor quantum dot, and the thickness of 0.105 mm was the same as in Example 1 except that the resin, solvent, and film drying conditions shown in Table 2 were employed. A wavelength conversion film was produced. Table 2 shows the production conditions of the wavelength conversion film.

Resin G: Cyclic Olefin Resin “Zeonor (registered trademark) 1420R” (manufactured by Nippon Zeon Co., Ltd.)
Resin H: Cyclic olefin-based resin “APEL (registered trademark) # 6015” (manufactured by Mitsui Chemicals, Inc.)
Resin I: Polycarbonate resin “Pure Ace (registered trademark)” (manufactured by Teijin Limited)
Resin J: Polyethersulfone resin “Sumilite (registered trademark) FS-1300” (manufactured by Sumitomo Bakelite Co., Ltd.)
Resin K: Heat-resistant acrylic resin “Acryview (registered trademark)” (manufactured by Nippon Shokubai Co., Ltd.)
Solvent (1): Methylene chloride Solvent (2): N, N-dimethylacetamide Solvent (3): Ethyl acetate / toluene (weight ratio: 5/5)
Solvent (4): cyclohexane / xylene (weight ratio: 7/3)
Solvent (5): cyclohexane / methylene chloride (weight ratio: 99/1)
Solvent (6): N-methyl-2-pyrrolidone

  Moreover, the film drying conditions of Example 1-Example 55 in Table 1 and Table 2 are as follows.

Condition (1): 20 ° C./8 hr → under reduced pressure 100 ° C./8 hr
Condition (2): 60 ° C./8 hr → 80 ° C./8 hr → under reduced pressure 140 ° C./8 hr
Condition (3): 60 ° C./8 hr → 80 ° C./8 hr → under reduced pressure 100 ° C./24 hr
Condition (4): 40 ° C./4 hr → 60 ° C./4 hr → under reduced pressure 100 ° C./8 hr

  Each of the wavelength conversion films obtained in Examples 2 to 11 was used, and blue light having a peak wavelength of 450 nm was irradiated using a blue LED. As a result, it was confirmed that some wavelength conversion of excitation light was performed in each wavelength conversion film, and red light was emitted.

  Each of the wavelength conversion films obtained in Examples 12 to 22 was used, and blue light having a peak wavelength of 450 nm was irradiated using a blue LED. As a result, it was confirmed that some wavelength conversion of excitation light was performed in each wavelength conversion film, and red light was emitted.

  Each of the wavelength conversion films obtained in Examples 23 to 33 was used, and blue light having a peak wavelength of 450 nm was irradiated using a blue LED. As a result, it was confirmed that some wavelength conversion of excitation light was performed in each wavelength conversion film, and red light was emitted.

  Each of the wavelength conversion films obtained in Examples 34 to 44 was used, and blue light having a peak wavelength of 450 nm was irradiated using a blue LED. As a result, it was confirmed that some wavelength conversion of excitation light was performed in each wavelength conversion film, and red light was emitted.

  Each of the wavelength conversion films obtained in Example 45 to Example 55 was used, and blue light having a peak wavelength of 450 nm was irradiated using a blue LED. As a result, it was confirmed that some wavelength conversion of excitation light was performed in each wavelength conversion film, and red light was emitted.

  The wavelength conversion film of the present invention is excellent in stability, and can be used in the fields of LEDs and solar cells in addition to display elements and electronic devices using the display elements.

1, 11 Wavelength conversion substrate 2, 12, 16 Base material 3, 13a, 13b, 13c, 102 Wavelength conversion film 14 Black matrix 15 Adhesive layer 17a, 17b, 17c, 101 Light source 18 Light source substrate 100 Display element 103 Holding body 104 Diffuser 200 Lighting device

Claims (7)

Including semiconductor quantum dots and resins,
The resin, cyclic polyolefin resin, aromatic polyether-based resins, full Oren polycarbonate resin, fluorene polyester resins, at least one selected from Po Li polyethersulfone-based resins, or Ranaru group A wavelength conversion film characterized by being. The semiconductor quantum dot is
At least one selected from the group consisting of InP / ZnS, CuInS2 / ZnS, and (ZnS / AgInS2) solid solution / ZnS that are core-shell structured semiconductor quantum dots, and AgInS2 and Zn-doped AgInS2 that are homogeneous structured semiconductor quantum dots The wavelength conversion film according to claim 1, wherein the wavelength conversion film is provided.   The cyclic polyolefin resin is represented by the following formula (X ₀ ) And the following formula (Y ₀ 2) A resin obtained from at least one monomer selected from the group consisting of monomers represented by (1), or obtained by hydrogenating the resin as necessary. Or the wavelength conversion film of 2.
The above formula (X ₀ ), Rx1 to Rx4 each independently represents an atom or group selected from the following (i ') to (viii'), and kx, mx and px each independently represent 0 or a positive integer.
(I ′) hydrogen atom
(Ii ') a halogen atom
(Iii ') a trialkylsilyl group
(Iv ') a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms having a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom
(V ′) a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms
(Vi ') polar group (excluding (iv'))
(Vii ′) Rx1 and Rx2 or Rx3 and Rx4 represent an alkylidene group formed by bonding to each other, and Rx1 to Rx4 not involved in the bonding are independently the above (i ′) to (vi ′ ) Represents an atom or group selected from
(Viii ′) Rx1 and Rx2 or Rx3 and Rx4 each represent a monocyclic or polycyclic hydrocarbon ring or heterocycle formed by bonding to each other, and Rx1 to Rx4 not participating in the bonding are each independently Represents an atom or group selected from the above (i ′) to (vi ′), or Rx2 and Rx3 represent a monocyclic hydrocarbon ring or heterocyclic ring formed by bonding to each other, and Rx1 to Rx4 that are not involved each independently represent an atom or group selected from the above (i ′) to (vi ′).
  In the above formula (Y0), Ry1 and Ry2 each independently represent an atom or group selected from the above (i ′) to (vi ′) or the following (ix ′), and ky and py are respectively Independently represents 0 or a positive integer.
(Ix ') Ry1 and Ry2 each represent a monocyclic or polycyclic alicyclic hydrocarbon, aromatic hydrocarbon or heterocyclic ring formed by bonding to each other.   The aromatic polyether resin has at least one structural unit selected from the group consisting of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2). The wavelength conversion film according to claim 1 or 2.
  In said formula (1), R1-R4 shows a C1-C12 monovalent organic group each independently, and ad shows the integer of 0-4 each independently.
  In the above formula (2), R 1 to R 4 and a to d are independently the same as R 1 to R 4 and a to d in the formula (1), and Y is a single bond, —SO 2 — or> C═. O, R7 and R8 each independently represent a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group, g and h each independently represents an integer of 0 to 4, m is 0 or 1 is shown. However, when m is 0, R7 is not a cyano group.   The semiconductor quantum dot is made of a material (A) having a fluorescence maximum in a wavelength region of 500 nm to 600 nm and / or a material (B) having a fluorescence maximum in a wavelength region of 600 nm to 700 nm. 4. The wavelength conversion film according to any one of 3 above.   A wavelength conversion element comprising the wavelength conversion film according to claim 1.   A display element comprising the wavelength conversion film according to claim 1.