WO2021028977A1

WO2021028977A1 - Wavelength conversion material, method for manufacturing wavelength conevrsion material, laminate, backlight unit, and image display device

Info

Publication number: WO2021028977A1
Application number: PCT/JP2019/031689
Authority: WO
Inventors: 佳歩山口; 康平向垣内; 真弓佐藤
Original assignee: 昭和電工マテリアルズ株式会社
Priority date: 2019-08-09
Filing date: 2019-08-09
Publication date: 2021-02-18
Also published as: WO2021029240A1; TW202113028A

Abstract

Provided is a wavelength conversion material comprising: a wavelength conversion layer having a fluorescent body and a resin hardener; and covering materials disposed on both sides of the wavelength conversion layer, wherein a carrier film is disposed on an outer surface of at least one of the covering materials and is enabled to be peeled from said at least one of the covering materials.

Description

Wavelength conversion material, manufacturing method of wavelength conversion material, laminate, backlight unit, and image display device

The present disclosure relates to a wavelength conversion material, a method for manufacturing a wavelength conversion material, a laminate, a backlight unit, and an image display device.

In recent years, in the field of image display devices such as liquid crystal display devices, it has been required to improve the color reproducibility of displays. As a means for improving color reproducibility, for example, a wavelength conversion material containing a phosphor as described in Patent Document 1 and Patent Document 2 is attracting attention.

The wavelength conversion material containing the phosphor is arranged, for example, in the backlight unit of the image display device. When a wavelength conversion material containing a phosphor that emits red light and a phosphor that emits green light is used, when the wavelength conversion material is irradiated with blue light as excitation light, the red light emitted from the phosphor and White light can be obtained from green light and blue light transmitted through a wavelength conversion material. With the development of wavelength conversion materials containing phosphors, the color reproducibility of displays has been expanded from 72% of the conventional NTSC (National Television System Committee) ratio to 100% of the NTSC ratio.

Special Table 2013-544018 International Publication No. 2016/05/2625

Until now, wavelength conversion materials have been mainly used for relatively large displays such as televisions, but demand for small displays such as smartphones and tablets is expected to increase in the future. Therefore, it is considered that the wavelength conversion material will be made thinner (for example, the thickness is 150 μm or less) in order to make it compatible with a small display.

The wavelength conversion material generally includes a wavelength conversion layer containing a phosphor and a coating material arranged on both sides thereof, and the wavelength conversion layer is formed by curing a resin composition containing a phosphor. Therefore, when the wavelength conversion material is made thinner, the rigidity is lowered, and wrinkles due to curing shrinkage of the resin composition are likely to occur, which may impair the appearance.

In view of the above circumstances, it is an object of the present disclosure to provide a wavelength conversion material in which wrinkles are suppressed even if the thickness is thin, and a method for producing the same. Another object of the present disclosure is to provide a laminate used for manufacturing the wavelength conversion material, a backlight unit using the wavelength conversion material, and an image display device.

Means for solving the above problems include the following aspects.
<1> A wavelength conversion material comprising a wavelength conversion layer containing a phosphor and a cured resin product and coating materials arranged on both sides of the wavelength conversion layer, from the coating material on at least one outer surface of the coating material. A wavelength conversion material in which a peelable carrier film is placed.
<2> The wavelength conversion material according to <1>, wherein the peeling force of the carrier film from the coating material measured under the condition of a peeling speed of 300 mm / min is 0.7 N / 25 mm or less.
<3> The wavelength conversion material according to <1> or <2>, wherein the thickness of the coating material is 25 μm or less. <4> The thickness of the wavelength conversion material in a state where the carrier film is not arranged is 150 μm or less. The wavelength conversion material according to any one of <1> to <3>.
<5> The wavelength conversion material according to any one of <1> to <4>, wherein the thickness of the carrier film is 30 μm to 150 μm.
<6> The wavelength conversion material according to any one of <1> to <5>, wherein the wrinkle height in the state where the carrier film is not arranged is less than 3.0 mm.
<7> A wavelength that includes a wavelength conversion layer containing a phosphor and a cured resin, and coating materials arranged on both sides of the wavelength conversion layer, and the total thickness of the wavelength conversion layer and the coating material is 150 μm or less. Conversion material.
<8> The wavelength conversion material according to <7>, wherein the wrinkle height is less than 3.0 mm.
<9> The wavelength conversion material according to any one of <1> to <8>, which is in the form of a film.
<10> The wavelength conversion material according to any one of <1> to <9>, which is used for displaying an image.
<11> The wavelength conversion material according to any one of <1> to <10>, wherein the phosphor contains a quantum dot phosphor.
<12> The wavelength conversion material according to <11>, wherein the quantum dot phosphor contains a compound containing at least one of Cd and In.
<13> A resin composition layer containing a phosphor and a resin, a coating material arranged on both sides of the resin composition layer, and a carrier arranged on at least one outer surface of the coating material and peelable from the coating material. The process of preparing the laminate with the film and
A method for producing a wavelength conversion material, comprising a step of curing the resin composition layer of the laminate.
<14> Production of the wavelength conversion material according to any one of <1> to <12>, comprising a coating material and a carrier film arranged on one side of the coating material and removable from the coating material. Laminated body used for.
<15> A backlight unit including the wavelength conversion material according to any one of <1> to <13> and a light source.
<16> An image display device including the backlight unit according to <15>.

According to the present disclosure, a wavelength conversion material in which wrinkles are suppressed even if the thickness is thin and a method for producing the same are provided. Further, according to the present disclosure, a laminate used for manufacturing the wavelength conversion material, a backlight unit using the wavelength conversion material, and an image display device are provided.

It is a schematic cross-sectional view which shows an example of the schematic structure of the wavelength conversion material. It is a figure which shows an example of the schematic structure of the backlight unit. It is a figure which shows an example of the schematic structure of the liquid crystal display device.

Hereinafter, a mode for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the components (including element steps and the like) are not essential unless otherwise specified. The same applies to the numerical values and their ranges, and does not limit the present invention.

In the present disclosure, the numerical range indicated by using "-" includes the numerical values before and after "-" as the minimum value and the maximum value, respectively.
In the numerical range described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. .. Further, in the numerical range described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
In the present disclosure, each component may contain a plurality of applicable substances. When a plurality of substances corresponding to each component are present in the composition, the content rate or content of each component is the total content rate or content of the plurality of substances present in the composition unless otherwise specified. Means quantity.
In the present disclosure, a plurality of types of particles corresponding to each component may be contained. When a plurality of particles corresponding to each component are present in the composition, the particle size of each component means a value for a mixture of the plurality of particles present in the composition unless otherwise specified.
In the present disclosure, the term "layer" or "membrane" refers to only a part of the region, in addition to the case where the layer or the membrane is formed in the entire region when the region where the layer or the membrane exists is observed. The case where it is formed is also included.
In the present disclosure, the term "laminated" refers to stacking layers, and two or more layers may be bonded or the two or more layers may be removable.
In the present disclosure, "(meth) acrylate" means at least one of acrylate and methacrylate, "(meth) allyl" means at least one of allyl and metaallyl, and "(meth) acrylic" means acrylic and methacrylic. And "(meth) acryloyl" means at least one of acryloyl and methacryloyl.
When the embodiment is described in the present disclosure with reference to the drawings, the configuration of the embodiment is not limited to the configuration shown in the drawings. Further, the size of the members in each figure is conceptual, and the relative relationship between the sizes of the members is not limited to this. Further, in each drawing, members having substantially the same function may be given the same reference numerals in all drawings, and duplicate description may be omitted.

<< Wavelength converter (first embodiment) >>
The wavelength conversion material of the first embodiment is a wavelength conversion material including a wavelength conversion layer containing a phosphor and a cured resin product and a coating material arranged on both sides of the wavelength conversion layer, and at least one of the coating materials. It is a wavelength conversion material in which a carrier film that can be peeled off from the coating material is arranged on the outer surface of the above.

In the wavelength conversion material having the above configuration, a carrier film peelable from the coating material is arranged on at least one outer surface of the coating material arranged on both sides of the wavelength conversion layer. By arranging the carrier film, sufficient rigidity is ensured even if the thickness of the covering material itself is thin. As a result, wrinkles are less likely to occur due to volume shrinkage during curing of the resin composition, and a good appearance is maintained. Further, since the carrier film can be peeled off from the coating material, the carrier film can be removed when the carrier film is incorporated into an image display device or the like to reduce the thickness of the wavelength conversion material.

The wavelength conversion material of the present disclosure includes at least a wavelength conversion layer and a coating material. Hereinafter, the wavelength conversion material including the carrier film may be referred to as a “wavelength conversion material with a carrier film”.

The thickness of the wavelength conversion material with a carrier film is not particularly limited, and can be set in consideration of ensuring the required rigidity, handleability, and the like. For example, it may be in the range of 100 μm to 500 μm, in the range of 150 μm to 400 μm, or in the range of 200 μm to 300 μm.

From the viewpoint of compatibility with small displays, the smaller the thickness of the wavelength conversion material (total thickness of the wavelength conversion layer and the coating material), the more preferable. For example, it is preferably 150 μm or less, and more preferably 125 μm or less. On the other hand, from the viewpoint of obtaining a sufficient wavelength conversion function, the thickness of the wavelength conversion material is preferably 50 μm or more, and more preferably 75 μm or more.

From the viewpoint of achieving both thinning of the wavelength conversion material and suppression of wrinkles, a thicker carrier film is preferable. The thickness of the carrier film is, for example, preferably 30 μm or more, more preferably 38 μm or more, and further preferably 50 μm or more. The upper limit of the thickness of the carrier film is not particularly limited. From the viewpoint of economy, for example, it is preferably 150 μm or less, more preferably 125 μm or less, and further preferably 100 μm or less.
When the carrier films are arranged on the outer surfaces of both coatings, the thickness is the thickness of each carrier film. When the carrier film includes an adhesive layer described later, the above thickness is the thickness including the adhesive layer.

From the viewpoint of reducing the thickness of the wavelength conversion material, the thickness of the coating material is preferably 25 μm or less, and more preferably 20 μm or less. From the viewpoint of sufficiently protecting the wavelength conversion layer, the thickness of the coating material is preferably 5 μm or more, and more preferably 10 μm or more.
The above thickness is the thickness of each of the coating materials arranged on both sides of the wavelength conversion layer.

From the viewpoint of reducing the thickness of the wavelength conversion material, the thickness of the wavelength conversion layer is preferably 100 μm or less, more preferably 80 μm or less, and further preferably 75 μm or less. From the viewpoint of obtaining a sufficient wavelength conversion effect, the thickness of the wavelength conversion layer is preferably 50 μm or more, more preferably 60 μm or more, and further preferably 65 μm or more.

The thickness of the wavelength conversion material, the wavelength conversion layer, the coating material and the carrier film can be measured by using a known means such as a micrometer and an electron microscope. If the thickness is not constant, the arithmetic mean value of the thickness at any three locations is used as the thickness.

The carrier film is removed when the wavelength conversion material is incorporated into an image display device or the like. Therefore, it is preferable that the peelability from the coating material is excellent. Specifically, the peeling force from the coating material measured under the condition of a peeling speed of 300 mm / min is preferably 0.7 N / 25 mm or less, more preferably 0.5 N / 25 mm or less, and 0. It is more preferably 4N / 25 mm or less.

The peeling force is a value measured as follows.
The wavelength conversion material is cut into a width of 25 mm, and the carrier film is peeled off from the pressure-sensitive adhesive layer using a tensile tester under an atmosphere of a peeling angle of 180 degrees, a peeling speed of 300 mm / min, and a room temperature (25 ° C.). The peeling force (mN / 25 mm) at this time is measured.
Examples of the tensile tester include Tensilon RTA-100 (manufactured by Orientec, which is also used in Examples described later). However, other than this can be used.

The wavelength conversion material preferably has a wrinkle height of less than 3.0 mm, more preferably less than 1.5 mm. When the wrinkle height is less than 3.0 mm, the occurrence of wrinkles is sufficiently suppressed, and it can be judged that the appearance of the wavelength conversion material is sufficiently good. The wrinkle height of the wavelength conversion material is a value measured by the method described in Examples described later.

FIG. 1 shows an example of a schematic configuration of a wavelength conversion material with a carrier film. However, the wavelength conversion material of the present disclosure is not limited to the configuration shown in FIG.

The wavelength conversion material 10 with a carrier film shown in FIG. 1 includes a wavelength conversion layer 11 which is a cured product of a resin composition containing a phosphor,

coating materials

12A and 12B provided on both sides of the wavelength conversion layer 11, and a coating material. It has

carrier films

13A and 13B arranged on the outer surfaces of 12A and 12B.

In the configuration shown in FIG. 1, the

carrier films

13A and 13B are arranged on the outer surfaces of the covering

materials

12A and 12B, but the carrier film may be arranged only on the outer surface of either one of the covering

materials

12A and 12B.

The wavelength conversion material with a carrier film having the configuration shown in FIG. 1 can be manufactured by, for example, the following manufacturing method.

First, prepare a covering material (covering material with a carrier film) in which a carrier film is arranged on one side. The method of arranging the carrier film on one side of the covering material is not particularly limited. For example, the adhesive layer side of the carrier film having the adhesive layer formed on one side may be laminated on one side of the coating material.

Next, the resin composition for forming the wavelength conversion layer is applied to the surface opposite to the side on which the carrier film of the coating material is arranged to form the resin composition layer. Another coating material with a carrier film is arranged on the resin composition layer to obtain a laminate in which the carrier film, the coating material, the resin composition layer, the coating material, and the carrier film are arranged in this order.

Next, the resin composition layer is cured. The curing method is not particularly limited. For example, it can be carried out by irradiation with active energy rays that can transmit the carrier film and the coating material and can cure the resin contained in the resin composition layer.

By performing the curing treatment of the resin composition layer while the carrier film is arranged on the outer surface of the coating material, it is effective to generate wrinkles due to shrinkage of the resin composition layer during curing even if the coating material is thin. Is suppressed.

After the curing treatment, the laminate is cut to a desired size as needed. As a result, a wavelength conversion material with a carrier film having the configuration shown in FIG. 1 can be obtained.

<Wavelength conversion layer>
The wavelength conversion layer contains a phosphor and a cured resin product. By selecting the type of phosphor contained in the wavelength conversion layer, the wavelength of light incident on the wavelength conversion layer can be converted into a predetermined wavelength. For example, by including phosphors that convert blue light into red light and green light, the wavelength conversion layer can be combined with red light and green light in which a part of the blue light incident on the wavelength conversion layer is converted by the phosphor. White light can be obtained by the transmitted blue light.

(Fluorescent material)
The type of phosphor contained in the wavelength conversion layer is not particularly limited. For example, organic phosphors and inorganic phosphors can be mentioned.
Examples of the organic phosphor include a naphthalimide compound and a perylene compound.
Examples of the inorganic phosphor include Y ₃ O ₃ : Eu, YVO ₄ : Eu, Y ₂ O ₂ : Eu, 3.5 MgO / 0.5 MgF ₂ , GeO ₂ : Mn, (Y · Cd) BO ₂ : Eu, etc. Red light emitting inorganic fluorescent material, ZnS: Cu · Al, (Zn · Cd) S: Cu · Al, ZnS: Cu · Au · Al, Zn ₂ SiO ₄ : Mn, ZnSiO ₄ : Mn, ZnS: Ag · Cu, ( Zn · Cd) S: Cu, ZnS: Cu, GdOS: Tb, LaOS: Tb, YSiO ₄ : Ce · Tb, ZnGeO ₄ : Mn, GeMgAlO: Tb, SrGaS: Eu ²⁺ , ZnS: Cu · Co, MgO · nB ₂ O ₃ : Green luminescent inorganic phosphors such as Ge · Tb, LaOBr: Tb · Tm, La ₂ O ₂ S: Tb, ZnS: Ag, GaWO ₄ , Y ₂ SiO ₆ : Ce, ZnS: Ag · Ga · Cl , Ca ₂ B ₄ OCl: Eu ²⁺ , BaMgAl ₄ O ₃ : Eu ^{2+ and} other blue light emitting inorganic phosphors, quantum dot phosphors and the like.

From the viewpoint of color reproducibility of the image display device, it is preferable that the wavelength conversion layer contains a quantum dot phosphor as a phosphor. The type of the quantum dot phosphor is not particularly limited, and examples thereof include particles containing at least one selected from the group consisting of a group II-VI compound, a group III-V compound, a group IV-VI compound, and a group IV compound. .. From the viewpoint of luminous efficiency, the quantum dot phosphor preferably contains a compound containing at least one of Cd and In.

Specific examples of the II-VI group compounds include CdSe, CdTe, CdS, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSte, ZnSeS, ZnSeTe, ZnSte, HgSeS, ZnS. , CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSe, CdHgSe, CdHgSe, CdHgSe
Specific examples of Group III-V compounds include GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, COLP, PLGAs, PLACSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb , AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInNSb, GaInPAs, GaInPSb, AlInPAs, GaInPSb, InAl
Specific examples of the IV-VI group compounds include SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSte, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbSne, SnPbSe, SnPbSe ..
Specific examples of the Group IV compound include Si, Ge, SiC, and SiGe.

The quantum dot phosphor may have a core-shell structure. By making the band gap of the compound constituting the shell wider than the band gap of the compound constituting the core, it is possible to further improve the quantum efficiency of the quantum dot phosphor. Examples of the combination of core and shell (core / shell) include CdSe / ZnS, InP / ZnS, PbSe / PbS, CdSe / CdS, CdTe / CdS, CdTe / ZnS and the like.

The quantum dot phosphor may have a so-called core multi-shell structure in which the shell has a multi-layer structure. By stacking one or more layers of shells with a narrow bandgap on a core with a wide bandgap, and further stacking a shell with a wide bandgap on top of this shell, the quantum efficiency of the quantum dot phosphor can be further improved. Is possible.

When the wavelength conversion layer contains a phosphor, the wavelength conversion layer may contain one type of phosphor alone or a combination of two or more types of phosphors. Examples of a mode in which two or more types of phosphors are contained in combination include a mode in which two or more types of phosphors having different components but the same average particle size are contained, and a mode in which the average particle size is different but the components are the same. Examples thereof include an embodiment containing two or more types, and an embodiment containing two or more types of phosphors having different components and average particle diameters. The emission center wavelength of the phosphor can be changed by changing at least one of the components of the phosphor and the average particle size.

When the wavelength conversion layer contains a quantum dot phosphor as a phosphor, the proportion of the quantum dot phosphor is preferably 50% by mass or more, more preferably 70% by mass or more, and 80% by mass of the entire phosphor. It is more preferably% or more.

For example, even if the wavelength conversion layer contains a phosphor G having an emission center wavelength in the green wavelength region of 520 nm to 560 nm and a phosphor R having an emission center wavelength in the red wavelength region of 600 nm to 680 nm. Good. When the wavelength conversion layer containing the phosphor G and the phosphor R is irradiated with excitation light in the blue wavelength range of 430 nm to 480 nm, green light and red light are emitted from the phosphor G and the phosphor R, respectively. .. As a result, white light can be obtained by the green light and red light emitted from the phosphor G and the phosphor R and the blue light transmitted through the cured resin product.

The content of the phosphor in the wavelength conversion layer is, for example, preferably 0.01% by mass to 1.0% by mass, and 0.05% by mass to 0.5% by mass of the entire wavelength conversion layer. Is more preferable, and 0.1% by mass to 0.5% by mass is further preferable. When the content of the phosphor is 0.01% by mass or more of the entire wavelength conversion layer, a sufficient wavelength conversion function tends to be obtained, and the content of the phosphor is 1.0% by mass or less of the entire wavelength conversion layer. If this is the case, the aggregation of the phosphor tends to be suppressed.

(Resin cured product)
The type of the cured resin product contained in the wavelength conversion layer is not particularly limited. From the viewpoint of adhesion of the wavelength conversion layer to the coating material and suppression of wrinkles due to volume shrinkage during curing, the cured resin product preferably contains a sulfide structure. A cured resin product containing a sulfide structure can be obtained by curing a resin composition containing, for example, a thiol compound and a polymerizable compound having a carbon-carbon double bond that causes an thiol group to undergo an enthiol reaction.

From the viewpoint of heat resistance and moisture heat resistance of the wavelength conversion layer, the cured resin product preferably contains an alicyclic structure or an aromatic ring structure. The cured resin product having an alicyclic structure or an aromatic ring structure can be obtained, for example, by curing a resin composition containing a polymerizable compound having an alicyclic structure or an aromatic ring structure, which will be described later.

From the viewpoint of suppressing contact between the phosphor and oxygen, the cured resin product preferably contains an alkyleneoxy group. When the cured resin product contains an alkyleneoxy group, the polarity of the cured resin product increases, and non-polar oxygen tends to be difficult to dissolve in the components in the cured product. In addition, the flexibility of the cured resin product tends to increase and the adhesion to the coating material tends to improve.

The cured resin containing an alkyleneoxy group can be obtained, for example, by curing a resin composition containing a polymerizable compound having an alkyleneoxy group, which will be described later.

(Light diffuser)
The wavelength conversion layer may further contain a light diffusing material. By including the light diffusing material, the light incident on the wavelength conversion layer can be scattered and the wavelength conversion efficiency by the phosphor can be improved.

The type of light diffusing material contained in the wavelength conversion layer is not particularly limited, and examples thereof include titanium oxide, barium sulfate, zinc oxide, and calcium carbonate. Among these, titanium oxide is preferable from the viewpoint of light scattering efficiency. The titanium oxide may be rutile-type titanium oxide or anatase-type titanium oxide, and is preferably rutile-type titanium oxide.

When the light diffusing material contains titanium oxide, the proportion of titanium oxide is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass or more of the entire light diffusing material. preferable.

The amount of the light diffusing material in the wavelength conversion layer is not particularly limited, and can be adjusted according to the desired wavelength conversion efficiency, light transmittance, and the like. For example, the content of the light diffusing material is preferably 0.1% by mass to 10.0% by mass, more preferably 1.0% by mass to 7.5% by mass, and 2% by mass of the entire wavelength conversion layer. It is more preferably 0.0% by mass to 5.0% by mass.

The average particle size of the light diffusing material is preferably 0.1 μm to 1 μm, more preferably 0.2 μm to 0.8 μm, and even more preferably 0.2 μm to 0.5 μm.

In the present disclosure, the average particle size of the light diffusing material can be measured as follows.
The light diffusing material (extracted light diffusing material when contained in the wavelength conversion layer or the resin composition described later) is dispersed in purified water containing a surfactant to obtain a dispersion liquid. In the volume-based particle size distribution measured by a laser diffraction type particle size distribution measuring device (for example, Shimadzu Corporation, SALD-3000J) using this dispersion, the value when the integration from the small diameter side is 50% ( The median diameter (D50)) is defined as the average particle size (volume average particle size) of the light diffusing material. As a method for extracting the light diffusing material from the resin composition, for example, the resin composition can be obtained by diluting the resin composition with a liquid medium and precipitating the light diffusing material by centrifugation or the like to distribute the light diffusing material.
When the light diffusing material is contained in the wavelength conversion layer, the cross section of the wavelength conversion layer is observed by observing the particles using a scanning electron microscope, and the geometry equivalent to a circle (major axis and minor axis geometry) is observed for 50 particles. The average) may be calculated, and the value obtained as the arithmetic mean value may be used as the average particle size.

From the viewpoint of improving the dispersibility in the wavelength conversion layer, the light diffusing material preferably has an organic substance layer containing an organic substance on at least a part of the surface thereof. The organic substances contained in the organic substance layer include organic silane, organosiloxane, fluorosilane, organic phosphonate, organic phosphoric acid compound, organic phosphinate, organic sulfonic acid compound, carboxylic acid, carboxylic acid ester, carboxylic acid derivative, amide, and hydrocarbon. Examples thereof include waxes, polyolefins, copolymers of polyolefins, polyols, derivatives of polyols, alkanolamines, derivatives of alkanolamines, organic dispersants and the like.
The organic substance contained in the organic substance layer preferably contains a polyol, an organic silane, or the like, and more preferably contains at least one of the polyol or the organic silane.
Specific examples of organic silanes include octyltriethoxysilane, nonyltriethoxysilane, decyltriethoxysilane, dodecyltriethoxysilane, tridecyltriethoxysilane, tetradecyltriethoxysilane, pentadecyltriethoxysilane, and hexadecyltriethoxysilane. Examples thereof include silane, heptadecyltriethoxysilane, and octadecyltriethoxysilane.
Specific examples of the organosiloxane include polydimethylsiloxane (PDMS) terminated with a trimethylsilyl group, polymethylhydrosiloxane (PMHS), polysiloxane induced by functionalization of PMHS with an olefin (by hydrosilylation), and the like. ..
Specific examples of organic phosphonates include n-octylphosphonic acid and its ester, n-decylphosphonic acid and its ester, 2-ethylhexylphosphonic acid and its ester, and camphyl phosphonic acid and its ester.
Specific examples of the organic phosphoric acid compound include organic acidic phosphate, organic pyrophosphate, organic polyphosphate, organic metaphosphate, salts thereof and the like.
Specific examples of the organic phosphinate include n-hexylphosphinic acid and its ester, n-octylphosphinic acid and its ester, di-n-hexylphosphinic acid and its ester, and di-n-octylphosphinic acid and its ester. Can be mentioned.
Specific examples of the organic sulfonic acid compound include alkyl sulfonic acids such as hexyl sulfonic acid, octyl sulfonic acid, and 2-ethylhexyl sulfonic acid, these alkyl sulfonic acids, metal ions such as sodium, calcium, magnesium, aluminum, and titanium, and ammonium. Examples thereof include salts with ions and organic ammonium ions such as triethanolamine.
Specific examples of the carboxylic acid include maleic acid, malonic acid, fumaric acid, benzoic acid, phthalic acid, stearic acid, oleic acid, linoleic acid and the like.
Specific examples of the carboxylic acid ester include the above carboxylic acid, ethylene glycol, propylene glycol, trimethylolpropane, diethanolamine, triethanolamine, glycerol, hexanetriol, erythritol, mannitol, sorbitol, pentaerythritol, bisphenol A, hydroquinone, and flo. Examples thereof include esters and partial esters produced by reaction with a hydroxy compound such as loglucinol.
Specific examples of the amide include stearic acid amide, oleic acid amide, and erucic acid amide.
Specific examples of the polyolefin and its copolymer include a copolymer of polyethylene, polypropylene, ethylene and one or more compounds selected from propylene, butylene, vinyl acetate, acrylate, acrylamide and the like.
Specific examples of the polyol include glycerol, trimethylolethane, trimethylolpropane and the like.
Specific examples of alkanolamines include diethanolamine and triethanolamine.
Specific examples of the organic dispersant include high molecular weight organic dispersants having functional groups such as citric acid, polyacrylic acid, polymethacrylic acid, anionic, cationic, bidirectional and nonionic.

From the viewpoint of improving the dispersibility in the wavelength conversion layer, the light diffusing material may have an oxide layer containing an oxide in at least a part of the surface. Examples of the oxide contained in the oxide layer include silicon dioxide, aluminum oxide, zirconia, phosphoria, and boria. The oxide layer may be one layer or two or more layers. When the light diffusing material has two oxide layers, it preferably contains a first oxide layer containing silicon dioxide and a second oxide layer containing aluminum oxide.

When the light diffusing material has an organic material layer containing an organic substance and an oxide layer, it is preferable that the oxide layer and the organic material layer are provided on the surface of the light diffusing material in the order of the oxide layer and the organic material layer.
When the light diffusing material has an organic material layer and two oxide layers, a first oxide layer containing silicon dioxide, a second oxide layer containing aluminum oxide, and an organic material layer are formed on the surface of the light diffusing material. , The first oxide layer, the second oxide layer and the organic layer are provided in this order (the organic layer is the outermost layer).

The wavelength conversion layer may be a cured product of a composition (hereinafter, also simply referred to as a resin composition) containing a phosphor, a polymerizable compound, a photopolymerization initiator, and if necessary, a light diffusing material. Good. The resin composition preferably contains, as the polymerizable compound, a thiol compound and at least one selected from the group consisting of a (meth) acrylic compound and a (meth) allyl compound. The resin composition may optionally contain other components.

(Fluorescent material)
The details of the phosphor contained in the resin composition are as described above. The phosphor may be used in the state of a phosphor dispersion liquid dispersed in a dispersion medium. Examples of the dispersion medium for dispersing the phosphor include various organic solvents, silicone compounds, and monofunctional (meth) acrylate compounds. The fluorescent substance may be used in the state of a fluorescent substance dispersion liquid by using a dispersant, if necessary.

The organic solvent that can be used as the dispersion medium is not particularly limited unless precipitation and aggregation of the phosphor are confirmed, and acetonitrile, methanol, ethanol, acetone, 1-propanol, ethyl acetate, butyl acetate, toluene, etc. Examples include hexane.

Silicone compounds that can be used as a dispersion medium include straight silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil; amino-modified silicone oil, epoxy-modified silicone oil, carboxy-modified silicone oil, and carbinol-modified silicone. Oil, mercapto-modified silicone oil, heterogeneous functional group-modified silicone oil, polyether-modified silicone oil, methylstyryl-modified silicone oil, hydrophilic special-modified silicone oil, higher alkoxy-modified silicone oil, higher fatty acid-modified silicone oil, fluorine-modified silicone oil, etc. Modified silicone oil and the like.

The monofunctional (meth) acrylate compound that can be used as a dispersion medium is not particularly limited as long as it is liquid at room temperature (25 ° C.), and is a monofunctional (meth) acrylate compound having an alicyclic structure (preferably isobornyl). (Meta) acrylate and dicyclopentanyl (meth) acrylate), methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, ethoxylated o-phenylphenol (meth) acrylate and the like can be mentioned.

Examples of the dispersant used as needed include polyether amines (JEFFAMIN M-1000, HUNTSMAN) and the like.

The mass-based ratio of the phosphor to the phosphor dispersion is preferably 1% by mass to 20% by mass, and more preferably 1% by mass to 10% by mass.

The content of the phosphor dispersion liquid in the resin composition is, for example, relative to the total amount of the resin composition when the mass-based ratio of the phosphor to the phosphor dispersion liquid is 1% by mass to 20% by mass. It is preferably 1% by mass to 10% by mass, more preferably 4% by mass to 10% by mass, and further preferably 4% by mass to 7% by mass.
The content of the phosphor in the resin composition is preferably, for example, 0.01% by mass to 1.0% by mass, and 0.05% by mass to 0% by mass, based on the total amount of the resin composition. It is more preferably 5% by mass, and even more preferably 0.1% by mass to 0.5% by mass. When the content of the phosphor is 0.01% by mass or more, sufficient emission intensity tends to be obtained when the cured product is irradiated with excitation light, and when the content of the phosphor is 1.0% by mass or less. If there is, the aggregation of the phosphor tends to be suppressed.

(Polymerizable compound)
The resin composition contains a polymerizable compound. The polymerizable compound contained in the resin composition is not particularly limited, and examples thereof include a thiol compound, a (meth) acrylic compound, and a (meth) allyl compound. The (meth) allyl compound means a compound having a (meth) allyl group in the molecule, and the (meth) acrylic compound means a compound having a (meth) acryloyl group in the molecule. Compounds having both a (meth) allyl group and a (meth) acryloyl group in the molecule shall be classified as (meth) allyl compounds for convenience.

From the viewpoint of adhesion of the wavelength conversion layer to the coating material, the resin composition comprises a thiol compound as a polymerizable compound and at least one selected from the group consisting of a (meth) acrylic compound and a (meth) allyl compound. It is preferable to include it.

A cured product obtained by curing a resin composition containing a thiol compound as a polymerizable compound and at least one selected from the group consisting of a (meth) acrylic compound and a (meth) allyl compound has a thiol group and ( A sulfide structure (RSR', R and R'represents an organic group) formed by an entthiol reaction with a carbon-carbon double bond of a meta) acryloyl group or a (meth) allyl group. Including. As a result, the adhesion of the wavelength conversion layer to the coating material tends to be improved. Further, the optical characteristics of the wavelength conversion layer tend to be further improved.
Hereinafter, the thiol compound, the (meth) acrylic compound, and the (meth) allyl compound will be described in detail.

A. Thiol compound The thiol compound may be a monofunctional thiol compound having one thiol group in one molecule, or a polyfunctional thiol compound having two or more thiol groups in one molecule. The thiol compound contained in the resin composition may be only one kind or two or more kinds.

The thiol compound may or may not have a polymerizable group other than the thiol group (for example, (meth) acryloyl group, (meth) allyl group) in the molecule.
In the present disclosure, a compound containing a thiol group and a polymerizable group other than the thiol group in the molecule shall be classified as a "thiol compound".

Specific examples of the monofunctional thiol compound include hexanethiol, 1-heptanethiol, 1-octanethiol, 1-nonanthiol, 1-decanethiol, 3-mercaptopropionic acid, methyl mercaptopropionate, and methoxybutyl mercaptopropionate. Examples thereof include octyl mercaptopropionate, tridecyl mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate and the like.

Specific examples of the polyfunctional thiol compound include ethylene glycol bis (3-mercaptopropionate), diethylene glycol bis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), 1,2-. Propropylene glycol bis (3-mercaptopropionate), diethylene glycol bis (3-mercaptobutyrate), 1,4-butanediol bis (3-mercaptopropionate), 1,4-butanediol bis (3-mercaptobutyrate) Rate), 1,8-octanediol bis (3-mercaptopropionate), 1,8-octanediol bis (3-mercaptobutyrate), hexanediol bisthioglycolate, trimetylolpropanthris (3-mercaptopro) Pionate), trimethylolpropanetris (3-mercaptobutyrate), trimethylolpropanetris (3-mercaptoisobutyrate), trimethylolpropanetris (2-mercaptoisobutyrate), trimethylolpropanetristhioglycolate, Tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, trimethyl ethanetris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate) ), Pentaerythritol tetrakis (3-mercaptoisobutyrate), pentaerythritol tetrakis (2-mercaptoisobutyrate), dipentaerythritol hexakis (3-mercaptopropionate), dipentaerythritol hexakis (2-mercaptopro) Pionate), dipentaerythritol hexakis (3-mercaptobutyrate), dipentaerythritol hexakis (3-mercaptoisobutyrate), dipentaerythritol hexakis (2-mercaptoisobutyrate), pentaerythritol tetrakisthioglycol Rate, dipentaerythritol hexaxthioglycolate and the like can be mentioned.

The thiol compound preferably contains a polyfunctional thiol compound from the viewpoint of further improving the adhesion, heat resistance, and moist heat resistance of the wavelength conversion layer to the coating material. The ratio of the polyfunctional thiol compound to the total amount of the thiol compound is, for example, preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 100% by mass.

The thiol compound may be in the state of a thioether oligomer that has reacted with the (meth) acrylic compound. The thioether oligomer can be obtained by addition polymerization of a thiol compound and a (meth) acrylic compound in the presence of a polymerization initiator.

When the resin composition contains a thiol compound, the content of the thiol compound in the resin composition is preferably, for example, 5% by mass to 80% by mass, and 15% by mass, based on the total amount of the resin composition. It is more preferably to 70% by mass, and further preferably 20% by mass to 60% by mass.
When the content of the thiol compound is 5% by mass or more, the adhesion of the wavelength conversion layer to the coating material tends to be further improved, and when the content of the thiol compound is 80% by mass or less, the heat resistance of the wavelength conversion layer tends to be improved. The properties and moisture heat resistance tend to be further improved.

B. (Meta) Acrylic Compound The (meth) acrylic compound may be a monofunctional (meth) acrylic compound having one (meth) acryloyl group in one molecule, and two or more (meth) acrylic compounds in one molecule. It may be a polyfunctional (meth) acrylic compound having an acryloyl group. The (meth) acrylic compound contained in the resin composition may be one kind or two or more kinds.

Specific examples of the monofunctional (meth) acrylic compound include (meth) acrylic acid; methyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and isononyl (meth). ) Alkyl (meth) acrylate having an alkyl group having 1 to 18 carbon atoms such as acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate; benzyl (meth) acrylate, phenoxyethyl ( A (meth) acrylate compound having an aromatic ring such as a meta) acrylate; an alkoxyalkyl (meth) acrylate such as butoxyethyl (meth) acrylate; an aminoalkyl (meth) acrylate such as N, N-dimethylaminoethyl (meth) acrylate; Diethylene glycol monoethyl ether (meth) acrylate, triethylene glycol monobutyl ether (meth) acrylate, tetraethylene glycol monomethyl ether (meth) acrylate, hexaethylene glycol monomethyl ether (meth) acrylate, octaethylene glycol monomethyl ether (meth) acrylate, nona Polyalkylene glycol monoalkyl ether (meth) such as ethylene glycol monomethyl ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, heptapropylene glycol monomethyl ether (meth) acrylate, and tetraethylene glycol monoethyl ether (meth) acrylate. Acrylate; Polyalkylene glycol monoaryl ether (meth) acrylate such as hexaethylene glycol monophenyl ether (meth) acrylate; Cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, methylene oxide-added cyclo (Meta) acrylate compound having an alicyclic structure such as decatorien (meth) acrylate; (meth) acrylate compound having a heterocycle such as (meth) acryloylmorpholine and tetrahydrofurfuryl (meth) acrylate; heptadecafluorodecyl (meth) ) Alkyl fluoride (meth) acrylate such as acrylate; 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, trietylene Nglycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, hexaethylene glycol mono (meth) acrylate, octapropylene glycol mono (meth) acrylate and other (meth) acrylate compounds having hydroxyl groups; glycidyl (meth) acrylate A (meth) acrylate compound having a glycidyl group such as 2- (2- (meth) acryloyloxyethyloxy) ethyl isocyanate, a (meth) acrylate compound having an isocyanate group such as 2- (meth) acryloyloxyethyl isocyanate; tetra Polyalkylene glycol mono (meth) acrylates such as ethylene glycol mono (meth) acrylate, hexaethylene glycol mono (meth) acrylate, octapropylene glycol mono (meth) acrylate; (meth) acrylamide, N, N-dimethyl (meth) acrylamide. , N-Isopropyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide and other (meth) acrylamide compounds; Be done.

Specific examples of the polyfunctional (meth) acrylic compound include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonanediol di (meth) acrylate. Polyalkylene glycol di (meth) acrylate; Polyalkylene glycol di (meth) acrylate such as polyethylene glycol di (meth) acrylate and polypropylene glycol di (meth) acrylate; Trimethylol propantri (meth) acrylate, Trimethylol propantri with ethylene oxide (meth) Tri (meth) acrylate compounds such as meth) acrylate and tris (2-acryloyloxyethyl) isocyanurate; ethylene oxide-added pentaerythritol tetra (meth) acrylate, trimethylolpropanetetra (meth) acrylate, pentaerythritol tetra (meth) acrylate and the like. Tetra (meth) acrylate compounds; tricyclodecanedimethanol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, 1,3-adamantan dimethanol di (meth) acrylate, hydrogenated bisphenol A (poly) ethoxydi ( Meta) acrylate, hydrogenated bisphenol A (poly) propoxydi (meth) acrylate, hydrogenated bisphenol F (poly) ethoxydi (meth) acrylate, hydrogenated bisphenol F (poly) propoxydi (meth) acrylate, hydrogenated bisphenol S (poly) Examples thereof include (meth) acrylate compounds having an alicyclic structure such as ethoxydi (meth) acrylate and hydrogenated bisphenol S (poly) propoxydi (meth) acrylate.

The (meth) acrylic compound is preferably a (meth) acrylate compound having an alicyclic structure or an aromatic ring structure from the viewpoint of further improving the heat resistance and moisture heat resistance of the cured product. Examples of the alicyclic structure or aromatic ring structure include an isobornyl skeleton, a tricyclodecane skeleton, and a bisphenol skeleton.

The (meth) acrylic compound may be one having an alkyleneoxy group or a bifunctional (meth) acrylic compound having an alkyleneoxy group.

As the alkyleneoxy group, for example, an alkyleneoxy group having 2 to 4 carbon atoms is preferable, an alkyleneoxy group having 2 or 3 carbon atoms is more preferable, and an alkyleneoxy group having 2 carbon atoms is further preferable.
The alkyleneoxy group contained in the (meth) acrylic compound may be one type or two or more types.

The alkyleneoxy group-containing compound may be a polyalkyleneoxy group-containing compound having a polyalkyleneoxy group containing a plurality of alkyleneoxy groups.

When the (meth) acrylic compound has an alkyleneoxy group, the number of alkyleneoxy groups in one molecule is preferably 2 to 30, more preferably 2 to 20, and 3 to 20. The number is more preferably 10, and particularly preferably 3 to 5.

When the (meth) acrylic compound has an alkyleneoxy group, it preferably has a bisphenol structure. As a result, the heat resistance of the cured product tends to be superior. Examples of the bisphenol structure include a bisphenol A structure and a bisphenol F structure, and among them, the bisphenol A structure is preferable.

Specific examples of the (meth) acrylic compound having an alkyleneoxy group include alkoxyalkyl (meth) acrylates such as butoxyethyl (meth) acrylate; diethylene glycol monoethyl ether (meth) acrylate, and triethylene glycol monobutyl ether (meth) acrylate. Tetraethylene glycol monomethyl ether (meth) acrylate, hexaethylene glycol monomethyl ether (meth) acrylate, octaethylene glycol monomethyl ether (meth) acrylate, nonaethylene glycol monomethyl ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, Polyalkylene glycol monoalkyl ether (meth) acrylates such as heptapropylene glycol monomethyl ether (meth) acrylates and tetraethylene glycol monoethyl ether (meth) acrylates; polyalkylene glycol monoaryls such as hexaethylene glycol monophenyl ether (meth) acrylates. Ether (meth) acrylate; (meth) acrylate compound having a heterocycle such as tetrahydrofurfuryl (meth) acrylate; triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, hexaethylene glycol mono (meth) (Meta) acrylate compound having a hydroxyl group such as acrylate and octapropylene glycol mono (meth) acrylate; (meth) acrylate compound having a glycidyl group such as glycidyl (meth) acrylate; Polyethylene glycol di (meth) acrylate, polypropylene glycol di ( Polyalkylene glycol di (meth) acrylates such as meta) acrylates; tri (meth) acrylate compounds such as ethylene oxide-added trimethylol propantri (meth) acrylates; tetra (meth) acrylate compounds such as ethylene oxide-added pentaerythritol tetra (meth) acrylates. Examples thereof include bisphenol type di (meth) acrylate compounds such as ethoxylated bisphenol A type di (meth) acrylate, propoxylated bisphenol A type di (meth) acrylate, and propoxylated ethoxylated bisphenol A type di (meth) acrylate; ..
As the alkyleneoxy group-containing compound, ethoxylated bisphenol A type di (meth) acrylate, propoxylated bisphenol A type di (meth) acrylate and propoxylated ethoxylated bisphenol A type di (meth) acrylate are preferable, and ethoxylated bisphenol Type A di (meth) acrylate is more preferred.

When the resin composition contains a (meth) acrylic compound, the content of the (meth) acrylic compound in the resin composition is, for example, 40% by mass to 90% by mass with respect to the total amount of the resin composition. It may be 50% by mass to 80% by mass.

C. (Meta) Allyl Compound The (meth) allyl compound may be a monofunctional (meth) allyl compound having one (meth) allyl group in one molecule, and two or more (meth) allyl compounds in one molecule. It may be a polyfunctional (meth) allyl compound having an allyl group. The (meth) allyl compound contained in the resin composition may be only one kind or two or more kinds.

The (meth) allyl compound may or may not have a polymerizable group (for example, (meth) acryloyl group) other than the (meth) allyl group in the molecule.
In the present disclosure, compounds having a polymerizable group other than the (meth) allyl group in the molecule (excluding thiol compounds) shall be classified as "(meth) allyl compound".

Specific examples of the monofunctional (meth) allyl compound include (meth) allyl acetate, (meth) allyl n-propionate, (meth) allyl benzoate, (meth) allyl phenyl acetate, (meth) allyl phenoxy acetate, and (meth). Examples thereof include allyl methyl ether and (meth) allyl glycidyl ether.

Specific examples of the polyfunctional (meth) allyl compound include di (meth) allyl benzenedicarboxylate, di (meth) allyl cyclohexanedicarboxylate, di (meth) allylmaleate, di (meth) allyl adipate, and di (meth). Allyl phthalate, di (meth) allyl isophthalate, di (meth) allyl terephthalate, glycerin di (meth) allyl ether, trimethylpropandi (meth) allyl ether, pentaerythritol di (meth) allyl ether, 1,3-di (Meta) allyl-5-glycidyl isocyanurate, tri (meth) allyl cyanurate, tri (meth) allyl isocyanurate, tri (meth) allyl trimellitate, tetra (meth) allyl pyromeritate, 1, 3, 4 , 6-Tetra (meth) allyl glycol uryl, 1,3,4,6-tetra (meth) allyl-3a-methylglycoluryl, 1,3,4,6-tetra (meth) allyl-3a, 6a-dimethyl Glycol-uryl and the like can be mentioned.

Examples of the (meth) allyl compound include compounds having an isocyanurate skeleton such as tri (meth) allyl isocyanurate, tri (meth) allyl cyanurate, and benzenedicarboxylic acid di (meth) from the viewpoint of heat resistance and moisture heat resistance of the cured product. ) At least one selected from the group consisting of allyl and di (meth) allyl cyclohexanedicarboxylic acid is preferable, a compound having an isocyanurate skeleton is more preferable, and tri (meth) allyl isocyanurate is further preferable.

When the resin composition contains a (meth) allyl compound, the content of the (meth) allyl compound in the resin composition is, for example, 10% by mass to 50% by mass with respect to the total amount of the resin composition. It may be 15% by mass to 45% by mass.

In some embodiments, the polymerizable compound may include a thioether oligomer as a thiol compound and a (meth) allyl compound (preferably a polyfunctional (meth) allyl compound).

When the polymerizable compound contains a thioether oligomer and a (meth) allyl compound as a thiol compound and a phosphor is used as a phosphor, the phosphor may be in the state of a dispersion liquid dispersed in a silicone compound as a dispersion medium. preferable.

In some embodiments, the polymerizable compound comprises a thiol compound that is not in the form of a thioether oligomer and a (meth) acrylic compound (preferably a polyfunctional (meth) acrylic compound, more preferably a bifunctional (meth) acrylic compound). It may include.

When the polymerizable compound contains a thiol compound that is not in the state of a thioether oligomer and a (meth) acrylic compound and a quantum dot phosphor is used as the phosphor, the quantum dot phosphor is a (meth) acrylic as a dispersion medium. It is preferably in the state of a compound, preferably a monofunctional (meth) acrylic compound, more preferably a dispersion dispersed in isobornyl (meth) acrylate.

(Photopolymerization initiator)
The type of photopolymerization initiator contained in the resin composition is not particularly limited, and examples thereof include compounds that generate radicals when irradiated with active energy rays such as ultraviolet rays.

Specific examples of the photopolymerization initiator include benzophenone, N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1, 4,4'-bis (dimethylamino) benzophenone (also referred to as "Michler ketone"), 4,4'-bis (Diethylamino) benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 1-hydroxycyclohexylphenylketone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4- (4-) Aromatic ketone compounds such as (2-hydroxyethoxy) -phenyl) -2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one; alkyl Kinone compounds such as anthraquinone and phenanthrenquinone; benzoin compounds such as benzoin and alkylbenzoin; benzoin ether compounds such as benzoin alkyl ether and benzoin phenyl ether; benzyl derivatives such as benzyl dimethyl ketal; 2- (o-chlorophenyl) -4,5 -Diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl)- 2,4,5-Triarylimidazole dimer such as 4,5-diphenylimidazole dimer; aclysine derivatives such as 9-phenylacidine, 1,7- (9,9'-acrydinyl) heptane; 1,2 -Octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -1- Oxime ester compounds such as (O-acetyloxime); coumarin compounds such as 7-diethylamino-4-methylcoumarin; thioxanthone compounds such as 2,4-diethylthioxanthone; 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2,4,6-trimethylbenzoyl Acylphosphine oxide compounds such as -phenyl-ethoxy-phosphine oxide; and the like. The resin composition may contain one kind of photopolymerization initiator alone, or may contain two or more kinds of photopolymerization initiators in combination.

From the viewpoint of curability, the photopolymerization initiator is preferably at least one selected from the group consisting of an acylphosphine oxide compound, an aromatic ketone compound, and an oxime ester compound, from the acylphosphine oxide compound and the aromatic ketone compound. At least one selected from the above group is more preferable, and an acylphosphine oxide compound is further preferable.

The content of the photopolymerization initiator in the resin composition is preferably, for example, 0.1% by mass to 5% by mass, preferably 0.1% by mass to 3% by mass, based on the total amount of the resin composition. It is more preferably 0.1% by mass to 1.5% by mass. When the content of the photopolymerization initiator is 0.1% by mass or more, the sensitivity of the resin composition tends to be sufficient, and when the content of the photopolymerization initiator is 5% by mass or less, the resin The influence on the hue of the composition and the decrease in storage stability tend to be suppressed.

(Light diffuser)
The details of the light diffusing material contained in the resin composition are as described above.

(Other ingredients)
The resin composition may further contain components other than the above-mentioned components. For example, the resin composition may further contain components such as a solvent, a dispersion medium, a polymerization inhibitor, a silane coupling agent, a surfactant, an adhesion imparting agent, and an antioxidant. As for each component, one type may be used alone or two or more types may be used in combination.

(Method for preparing resin composition)
The resin composition can be prepared by mixing a phosphor, a polymerizable compound, a photopolymerization initiator, and if necessary, other components by a conventional method.

The wavelength conversion layer may be one obtained by curing one kind of resin composition, or may be one obtained by curing two or more kinds of resin compositions. For example, when the wavelength conversion material is in the form of a film, the wavelength conversion layer has different emission characteristics from the first cured product layer obtained by curing the resin composition containing the first phosphor and the first phosphor. A resin composition containing a second phosphor may be laminated with a second cured product layer obtained by curing the resin composition.

From the viewpoint of further improving the adhesion, the wavelength conversion layer preferably has a loss tangent (tan δ) of 0.4 to 1.5 measured under the conditions of a frequency of 10 Hz and a temperature of 25 ° C. by dynamic viscoelasticity measurement. It is more preferably 0.4 to 1.2, and even more preferably 0.4 to 0.6. The loss tangent (tan δ) of the wavelength conversion layer can be measured using a dynamic viscoelasticity measuring device (for example, Rheometric Scientific, Solid Analyzer RSA-III).

The wavelength conversion layer preferably has a glass transition temperature (Tg) of 85 ° C. or higher, more preferably 85 ° C. to 160 ° C., and 90 ° C., from the viewpoint of further improving adhesion, heat resistance, and moist heat resistance. It is more preferably ° C. to 120 ° C. The glass transition temperature (Tg) of the wavelength conversion layer can be measured under the condition of a frequency of 10 Hz using a dynamic viscoelasticity measuring device (for example, Rheometric Scientific, Solid Analyzer RSA-III).

The wavelength conversion layer has a storage elastic modulus of 1 × 10 ⁷ Pa to 1 × 10 ¹⁰ Pa measured under the conditions of a frequency of 10 Hz and a temperature of 25 ° C. from the viewpoint of further improving adhesion, heat resistance, and moisture heat resistance. It is preferably 5 × 10 ⁷ Pa to 1 × 10 ¹⁰ Pa, more preferably 5 × 10 ⁷ Pa to 5 × 10 ⁹ Pa. The storage elastic modulus of the cured resin can be measured using a dynamic viscoelasticity measuring device (for example, Rheometric Scientific, Solid Analyzer RSA-III).

The wavelength conversion layer can be obtained, for example, by forming a coating film, a molded product, or the like of a resin composition, performing a drying treatment as necessary, and then irradiating with active energy rays such as ultraviolet rays. The wavelength and irradiation amount of the active energy rays can be appropriately set according to the composition of the resin composition. In one aspect, it is irradiated with ultraviolet rays having a wavelength of 280 nm ~ 400 nm at an irradiation amount of ^{100mJ / cm 2 ~ 5000mJ / cm} 2. Examples of the ultraviolet source include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, black light lamps, microwave-excited mercury lamps, and the like.

<Coating material>
The covering material is arranged on both sides of the wavelength conversion layer. As a result, the invasion of water, oxygen, etc. into the wavelength conversion layer is suppressed, and the deterioration of the wavelength conversion layer is suppressed. In addition, appropriate rigidity is imparted to the wavelength conversion material to improve handleability.

The material of the covering material is not particularly limited, and polyester such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyolefin such as polyethylene (PE) and polypropylene (PP), polyamide such as nylon, and ethylene-vinyl alcohol co-weight. It may be coalescence (EVOH) or the like. From the viewpoint of availability, polyethylene terephthalate is preferable as the material of the covering material.

The covering material may be one provided with a barrier layer for strengthening the barrier function against water, oxygen, etc. (barrier film). Examples of the barrier layer include an inorganic layer containing an inorganic substance such as alumina and silica. When the covering material has a barrier layer, it is preferable that the barrier layer is arranged on the side in contact with the wavelength conversion layer.

Oxygen permeability of the dressing, for example, is preferably ^{1.0mL / (m 2 · 24h ·} atm) or less, more preferably ^{0.8mL / (m 2 · 24h ·} atm) or less, 0 and more preferably ^{.6mL / (m 2 · 24h ·} atm) or less. The oxygen permeability of the coating material can be measured using an oxygen permeability measuring device (for example, MOCON, OX-TRAN) under the conditions of a temperature of 23 ° C. and a relative humidity of 90%.

Further, the water vapor permeability of the dressing, for example, more that that 1 × ¹⁰ is ^{0 g / (m 2 · 24h} ) or less ^{^{preferably, 8 × 10 -1 g / (}} m 2 · 24h) or less preferably, and more preferably ^{^{6 × 10 -1 g / (m}} 2 · 24h) or less. The water vapor permeability of the coating material can be measured using a water vapor permeability measuring device (for example, MOCON, AQUATRAN) under the conditions of a temperature of 40 ° C. and a relative humidity of 100%.

<Carrier film>
The material of the carrier film is not particularly limited. For example, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyolefins such as polyethylene (PE) and polypropylene (PP), polyamides such as nylon, ethylene-vinyl alcohol copolymers (EVOH) and the like. May be good. From the viewpoint of availability, polyethylene terephthalate is preferable as the material of the covering material.

From the viewpoint of ensuring adhesion to the coating material, it is preferable that the carrier film has an adhesive layer on the surface in contact with the coating material. The adhesive layer preferably contains a pressure-sensitive adhesive such as an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, and a urethane-based pressure-sensitive adhesive, and more preferably contains an acrylic-based pressure-sensitive adhesive. The thickness of the adhesive layer is not particularly limited, and may be in the range of, for example, 1 μm to 10 μm.

<< Wavelength converter (second embodiment) >>
The wavelength conversion material of the second embodiment includes a wavelength conversion layer containing a phosphor and a cured resin product, and coating materials arranged on both sides of the wavelength conversion layer, and the total thickness of the wavelength conversion layer and the coating material. It is a wavelength conversion material having a wavelength of 150 μm or less.

The details and preferred embodiments of the wavelength conversion material, wavelength conversion layer and coating material of the second embodiment are the same as the details and preferred embodiments of the wavelength conversion material, wavelength conversion layer and coating material of the first embodiment.

In the wavelength conversion material of the second embodiment, a carrier film may be arranged on at least one outer surface of the covering material. The details and preferred embodiments of the carrier film are the same as the details and preferred embodiments of the carrier film included in the wavelength conversion material of the first embodiment.

≪Manufacturing method of wavelength conversion material≫
In the method for producing a wavelength conversion material of the present disclosure, a resin composition layer containing a phosphor and a resin, a coating material arranged on both sides of the resin composition layer, and at least one outer surface of the coating material are arranged. A method for producing a wavelength conversion material, comprising a step of preparing a laminate including a carrier film peelable from the coating material and a step of curing the resin composition layer of the laminate.

In the above method, the resin composition is cured with the carrier film arranged on at least one outer surface of the covering material. Therefore, even if the thickness of the wavelength conversion material is thin, the generation of wrinkles due to volume shrinkage during curing of the resin composition is suppressed, and a wavelength conversion material having a good appearance can be produced.

In the above method, the step of preparing the laminate including the resin composition layer, the coating material, and the carrier film is not particularly limited.
For example, the resin composition may be applied onto a coating material on which a carrier film is arranged on one side to form a resin composition layer, and another coating material may be arranged on the resin composition layer.

The method of arranging the carrier film on one side of the covering material is not particularly limited. For example, the adhesive layer side of the carrier film having the adhesive layer may be laminated on the coating material.

In the above method, the method of curing the resin composition layer is not particularly limited. For example, the resin composition layer may be irradiated with active energy rays that are transparent to the coating material and the carrier film and can be cured.

The above method may be a method for producing the wavelength conversion material of the present disclosure. That is, the details and preferred embodiments of the wavelength converting material produced by the above method may be the same as the details and preferred embodiments of the wavelength converting material of the present disclosure.

≪Laminated body≫
The laminate of the present disclosure is a laminate that includes a coating material and a carrier film that is arranged on one side of the coating material and can be peeled off from the coating material, and is used in the production of the wavelength conversion material described above.

The laminate is used in the production of the wavelength conversion material of the present disclosure. By arranging the carrier film on one side of the covering material, it is possible to suppress the occurrence of wrinkles in the manufacturing process of the wavelength conversion material. Further, by removing the carrier film from the coating material at an arbitrary time after the manufacturing process, a wavelength conversion material having a thin thickness can be obtained.

The details and preferred embodiments of the coating material and carrier film constituting the laminate are the same as the details and preferred embodiments of the coating material and carrier film constituting the wavelength conversion material described above.

≪Backlight unit≫
The backlight unit of the present disclosure includes a light source and a wavelength conversion material of the present disclosure.

The backlight unit is preferably a multi-wavelength light source from the viewpoint of improving color reproducibility. In a preferred embodiment, blue light having an emission center wavelength in the wavelength range of 430 nm to 480 nm and having an emission intensity peak having a half-value width of 100 nm or less, and emission center wavelength in the wavelength range of 520 nm to 560 nm. A back that emits green light having an emission intensity peak having a half-value width of 100 nm or less and red light having an emission center wavelength in the wavelength range of 600 nm to 680 nm and having an emission intensity peak having a half-value width of 100 nm or less. The light unit can be mentioned. The half-value width of the emission intensity peak means the peak width at a height of 1/2 of the peak height.

From the viewpoint of further improving the color reproducibility, the emission center wavelength of the blue light emitted by the backlight unit is preferably in the range of 440 nm to 475 nm. From the same viewpoint, the emission center wavelength of the green light emitted by the backlight unit is preferably in the range of 520 nm to 545 nm. From the same viewpoint, the emission center wavelength of the red light emitted by the backlight unit is preferably in the range of 610 nm to 640 nm.

Further, from the viewpoint of further improving the color reproducibility, the half-value width of each emission intensity peak of the blue light, green light, and red light emitted by the backlight unit is preferably 80 nm or less, preferably 50 nm or less. It is more preferably 40 nm or less, particularly preferably 30 nm or less, and extremely preferably 25 nm or less.

As the light source of the backlight unit, for example, a light source that emits blue light having a emission center wavelength in the wavelength range of 430 nm to 480 nm can be used. Examples of the light source include an LED (Light Emitting Diode) and a laser. When a light source that emits blue light is used, the wavelength conversion material preferably contains at least a phosphor R that emits red light and a phosphor G that emits green light. As a result, white light can be obtained from the red light and green light emitted from the wavelength conversion material and the blue light transmitted through the wavelength conversion material.

Further, as the light source of the backlight unit, for example, a light source that emits ultraviolet light having a emission center wavelength in the wavelength range of 300 nm to 430 nm can be used. Examples of the light source include LEDs and lasers. When a light source that emits ultraviolet light is used, the wavelength conversion material preferably contains a phosphor B that is excited by excitation light and emits blue light, together with the phosphor R and the phosphor G. As a result, white light can be obtained from the red light, green light, and blue light emitted from the wavelength conversion material.

The backlight unit of the present disclosure may be an edge light type or a direct type. FIG. 2 shows an example of a schematic configuration of an edge light type backlight unit. The backlight unit 20 shown in FIG. 2 includes a light source 21 for emitting the blue light L _B, a light guide plate 22 to be emitted guiding the blue light L _B emitted from the light source 21, the light guide plate 22 and disposed to face The wavelength conversion material 10 is provided with a retroreflective member 23 arranged to face the light source plate 22 via the wavelength conversion material 10, and a reflection plate 24 arranged to face the wavelength conversion material 10 via the light guide plate 22. .. Wavelength converting material 10 emits the red light L _R and the green light L _G part of the blue light L _B as the excitation light, the red light L and _R and the green light L _G, the blue light was not the excitation light L _B is emitted. The red light _{L R,} the green light _{L G,} and the blue light _{L B,} the white light _{L W} is emitted from the retroreflective member 23.

≪Image display device≫
The image display device of the present disclosure includes the backlight unit of the present disclosure described above. The image display device is not particularly limited, and examples thereof include a liquid crystal display device.

FIG. 3 shows an example of the schematic configuration of the liquid crystal display device. The liquid crystal display device 30 shown in FIG. 3 includes a backlight unit 20 and a liquid crystal cell unit 31 arranged to face the backlight unit 20. The liquid crystal cell unit 31 has a configuration in which the liquid crystal cell 32 is arranged between the polarizing plate 33A and the polarizing plate 33B.

The drive method of the liquid crystal cell 32 is not particularly limited, and is a TN (Twisted Nematic) method, an STN (Super Twisted Nematic) method, a VA (Virtical Birefringence) method, an IPS (In-Plane-Switching) method, an OCB (Optical Reference) method. The method and the like can be mentioned.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.

(Preparation of resin composition for wavelength conversion layer)
A resin composition for forming a wavelength conversion layer was prepared by mixing each component shown in Table 1 in a blending amount (unit: parts by mass) shown in the same table.

As the polyfunctional acrylic compound, tricyclodecanedimethanol diacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., A-DCP) was used.
As the polyfunctional thiol compound, pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by SC Organic Chemistry Co., Ltd., PEMP) was used.
As the photopolymerization initiator, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (IRGACURE TPO manufactured by BASF) was used. As the light diffusing material, titanium oxide (manufactured by The Chemours Company, Typure R-706, volume average particle size 0.36 μm) was used.
Examples of the quantum dot phosphor include a Gen3.5 QDC dispersion (core / shell: CdSe / ZnS, peak wavelength 532 nm) dispersion (Nanosys, Gen3.5 QD Concentrate) as a quantum dot phosphor G that emits green light. A Gen3.5 QDC dispersion (core / shell: InP / ZnS, peak wavelength 628 nm) dispersion (Gen3.5 QD Concentrate, manufactured by Nanosys) was used as the quantum dot phosphor R that emits red light.

(Preparation of coating material with carrier film)
A pressure-sensitive adhesive composition was prepared by blending 100 parts by mass of a pressure-sensitive adhesive, 15.0 parts by mass of a cross-linking agent, 0.1 parts by mass of a catalyst, and 100 parts by mass of a solvent (toluene) and stirring with a disper.

As the pressure-sensitive adhesive, an acrylic pressure-sensitive adhesive (copolymer of butyl acrylate (BA) and 4-hydroxybutyl acrylate (4HBA), solid content 24% by mass) was used.
As the catalyst, a tin-based catalyst (trade name "KS-1200A-1", Kyodo Yakuhin Co., Ltd.) was used.
As the cross-linking agent, polyfunctional isocyanate (trade name "Coronate HL", solid content 75% by mass, Tosoh Corporation, trimethylolpropane / hexamethylene diisocyanate trimer adduct 75% ethyl acetate solution, isocyanate in one molecule The number of bases: 3) was used.

The pressure-sensitive adhesive composition was applied to one side of a PET base material (A4300, double-sided easy-adhesive treatment, Toyobo Co., Ltd.) having the thickness shown in Table 2 below, dried at 100 ° C. for 1 minute, and had a thickness of 5 μm after drying. A carrier film having an adhesive layer formed on one side was produced.
Next, the adhesive layer side of the carrier film was laminated on the surface of the coating material having the thickness shown in Table 2 (PET base material having a barrier layer on one side, Dai Nippon Printing Co., Ltd.) on the side opposite to the surface on which the barrier layer was formed. Then, a covering material with a carrier film was produced.
The peeling force of the carrier film from the coating material of the produced coating material with a carrier film was measured by the method described above. The results are shown in Table 2.

(Manufacturing of wavelength conversion material)
A resin composition for a wavelength conversion layer was applied to a surface opposite to the side on which the carrier film of the prepared coating material with a carrier film was arranged to form a coating film. On this coating film, the surface opposite to the side on which the carrier film of the coating material with another carrier film is arranged is bonded, and ultraviolet rays are irradiated using an ultraviolet irradiation device (Igraphics Co., Ltd.) (irradiation amount: 1000 mJ). / Cm ² ) and the resin composition was cured to prepare a wavelength conversion material with a carrier film. Table 2 shows the thickness of the wavelength conversion material and the thickness of the wavelength conversion layer in the state where the carrier film is peeled off from the wavelength conversion material with the carrier film, respectively.
At the same time, a wavelength conversion layer of Comparative Example was produced in the same manner as in Example except that a covering material to which the carrier film was not laminated was used.

(Evaluation of wrinkle occurrence)
Place the wavelength conversion material (A4 size) from which the carrier film has been peeled off on a flat table, and check the presence or absence of wrinkles and the height of the wrinkles (the surface and table of the wavelength conversion material at the place where the wrinkles occur). The longest distance) was measured. Then, the state of wrinkles was evaluated according to the following evaluation criteria.

A: No wrinkles B: Wrinkle height less than 1.5 mm C: Wrinkle height 1.5 mm or more and less than 3.0 mm D: Wrinkle height 3.0 mm or more

As shown in Table 2, the wavelength conversion materials of Examples 1 to 3 using the coating material with a carrier film as the coating material suppress the occurrence of wrinkles even when the thickness of the wavelength conversion material is thin (100 μm). Was there. Further, the thicker the carrier film, the more effectively the occurrence of wrinkles was suppressed.
The wavelength conversion material of Comparative Example 1 in which the covering material to which the carrier film was not laminated was used and the thickness was the same as that of the example showed remarkable wrinkles. From the results of Comparative Examples 1 to 3, it was found that it is difficult to suppress the occurrence of wrinkles and reduce the thickness of the wavelength conversion material without using a carrier film.

All documents, patent applications, and technical standards described herein are to the same extent as if the individual documents, patent applications, and technical standards were specifically and individually stated to be incorporated by reference. Incorporated herein by reference.

Claims

A wavelength conversion material comprising a wavelength conversion layer containing a phosphor and a cured resin product and coating materials arranged on both sides of the wavelength conversion layer, and can be peeled off from the coating material on at least one outer surface of the coating material. A wavelength conversion material in which a carrier film is placed.
The wavelength conversion material according to claim 1, wherein the peeling force of the carrier film from the coating material measured under the condition of a peeling speed of 300 mm / min is 0.7 N / 25 mm or less.
The wavelength conversion material according to claim 1 or 2, wherein the thickness of the covering material is 25 μm or less.
The wavelength conversion material according to any one of claims 1 to 3, wherein the thickness of the wavelength conversion material in a state where the carrier film is not arranged is 150 μm or less.
The wavelength conversion material according to any one of claims 1 to 4, wherein the thickness of the carrier film is 30 μm to 150 μm.
The wavelength conversion material according to any one of claims 1 to 5, wherein the wrinkle height in the state where the carrier film is not arranged is less than 3.0 mm.
A wavelength conversion material comprising a wavelength conversion layer containing a phosphor and a cured resin product and coating materials arranged on both sides of the wavelength conversion layer, and the total thickness of the wavelength conversion layer and the coating material is 150 μm or less.
The wavelength conversion material according to claim 7, wherein the wrinkle height is less than 3.0 mm.
The wavelength conversion material according to any one of claims 1 to 8, which is in the form of a film.
The wavelength conversion material according to any one of claims 1 to 9, which is for displaying an image.
The wavelength conversion material according to any one of claims 1 to 10, wherein the phosphor contains a quantum dot phosphor.
The wavelength conversion material according to claim 11, wherein the quantum dot phosphor contains a compound containing at least one of Cd and In.
A resin composition layer containing a phosphor and a resin, a coating material arranged on both sides of the resin composition layer, and a carrier film arranged on at least one outer surface of the coating material and peelable from the coating material. And the process of preparing a laminate
A method for producing a wavelength conversion material, comprising a step of curing the resin composition layer of the laminate.
It is used for producing the wavelength conversion material according to any one of claims 1 to 12, comprising a coating material and a carrier film arranged on one side of the coating material and peelable from the coating material. , Laminated body.
A backlight unit including the wavelength conversion material according to any one of claims 1 to 13 and a light source.
An image display device including the backlight unit according to claim 15.