JP6302387B2 - Method for manufacturing wavelength conversion member, wavelength conversion member, backlight unit, and liquid crystal display device - Google Patents

Description

  The present invention relates to a method for manufacturing a wavelength conversion member, a wavelength conversion member, a backlight unit, and a liquid crystal display device. More specifically, a method for producing a wavelength conversion member, a wavelength conversion member, and a back that have good adhesion after wet heat aging between a wavelength conversion layer containing a quantum dot that is excited by excitation light and emits fluorescence and a barrier film The present invention relates to a light unit and a liquid crystal display device.

  Flat panel displays such as liquid crystal display devices (hereinafter also referred to as LCDs (Liquid Crystal Displays)) have low power consumption and are increasingly used year by year as space-saving image display devices. The liquid crystal display device is composed of at least a backlight and a liquid crystal cell, and usually further includes members such as a backlight side polarizing plate and a viewing side polarizing plate.

  In the flat panel display market, color reproducibility is improving as LCD performance improvement. In this regard, in recent years, quantum dots (also referred to as Quantum Dot, QD, quantum dots) have attracted attention as light emitting materials. For example, when excitation light enters the wavelength conversion member including quantum dots from the backlight, the quantum dots are excited and emit fluorescence. Here, by using quantum dots having different emission characteristics, white light can be realized by emitting red light, green light, and blue light. Since the fluorescence due to the quantum dots has a small half-value width, the white light obtained has high brightness and excellent color reproducibility. With the progress of the three-wavelength light source technology using such quantum dots, the color gamut is changed from 72% to 100% of the current television standard (FHD (Full High Definition), NTSC (National Television System Committee)). It is expanding.

JP 2011-46046 A

As a wavelength conversion member, the thing of the laminated structure which provided the barrier film which has one or more inorganic layers on the one or both main surfaces (the main surface is mentioned later) of the wavelength conversion layer containing a quantum dot can be considered. However, when the present inventors actually examined a wavelength conversion member having a barrier film, the adhesion between the wavelength conversion layer and the inorganic layer adjacent to this layer was not sufficient.
When the adhesion between the wavelength conversion layer and the inorganic layer adjacent to this layer is not sufficient, for example, when processing the wavelength conversion member to a specified size for shipping as a product (for example, punching with a punching device), Peeling occurs at the interface edge between the wavelength conversion layer and the inorganic layer. For example, as an example, in the case of a barrier film in which the inorganic layer is a layer having an oxygen barrier property, when such separation at the interface end occurs, the emission efficiency of the quantum dots decreases due to the intrusion of oxygen from the interface end. Is concerned. In addition, the insufficient adhesion between the wavelength conversion layer and the inorganic layer causes a decrease in durability of the member due to partial peeling between the layers.
In recent years, there has been an increasing demand for using a flat panel display such as a liquid crystal display device under humid heat environment conditions such as in-vehicle use and outdoor installation in summer. It was found that the adhesiveness between the wavelength conversion layer and the inorganic layer adjacent to this layer tends to be further lowered.

  On the other hand, a technique for providing adhesion between layers by adding a silane coupling agent to a monomer layer has been disclosed (for example, see Patent Document 1). In Patent Document 1, a base film, an organic layer, and an inorganic layer are included in this order, the thickness of the organic layer is 300 nm to 2000 nm, and the surface of the organic layer satisfies predetermined Ra and Rz. And the laminated film in which the inorganic layer contains the silicon oxide represented by SiOx (x is 0.9-1.5) is disclosed. According to this document, when the organic layer contains a silane coupling agent, the adhesion between the base material and the organic layer and between the organic layer and the inorganic layer can be improved, and the deterioration of the barrier performance due to the peeling failure can be reduced. It is described as.

  The problem to be solved by the present invention is to provide a method for producing a wavelength conversion member having good adhesion after wet heat aging between a wavelength conversion layer containing quantum dots and a barrier film.

As a result of intensive studies to solve the above problems, the inventors of the present invention have previously made the surface of the inorganic layer of the barrier film organic before laminating the inorganic layer of the barrier film and the wavelength conversion layer containing quantum dots. The structure which adds a silane coupling agent to the wavelength conversion layer of the wavelength conversion member which has a barrier film of the structure similar to patent document 1 (after-mentioned) by surface-treating with the composition containing a metal coupling agent and water. It has been found that the adhesiveness after wet heat aging can be improved with a configuration completely different from Reference Example 1).
The present invention, which is a specific means for solving the above problems, and preferred embodiments thereof are as follows.

[1] a surface treatment step of surface-treating a barrier film having at least one inorganic layer;
A lamination step of laminating a wavelength conversion layer containing quantum dots on the surface-treated surface of the barrier film,
The method for producing a wavelength conversion member, wherein the surface treatment step is a step of applying a composition for surface treatment containing a solvent containing water and an organic metal coupling agent to the surface of the inorganic layer of the barrier film. .
[2] In the method for producing a wavelength conversion member according to [1], the organometallic coupling agent preferably has a reactive functional group at the terminal.
[3] In the method for producing a wavelength conversion member according to [1] or [2], it is preferable that the composition for surface treatment described above contains a surfactant.
[4] In the method for producing a wavelength conversion member according to [3], the aforementioned surfactant is preferably a fluorine-based nonionic surfactant.
[5] In the method for producing a wavelength conversion member according to any one of [1] to [4], an organic solvent is preferably contained in the solvent for the surface treatment composition described above.
[6] In the method for producing a wavelength conversion member according to any one of [1] to [5], the surface treatment step includes a first barrier film having at least one inorganic layer and at least one layer. It is a step of surface-treating each second barrier film having an inorganic layer,
The laminating step is preferably a step of sandwiching the wavelength conversion layer between the surface-treated surfaces of the first barrier film and the second barrier film.
[7] The method for producing a wavelength conversion member according to [6] includes a step of unwinding the first barrier film and the second barrier film from the roll, respectively, before the surface treatment step.
Including the step of winding the wavelength converting member on a roll after the laminating step,
It is preferable to perform the above-mentioned unwinding process, the above-mentioned surface treatment process, the above-mentioned lamination process, and the above-mentioned winding-up process by a roll to roll.
[8] In the method for producing a wavelength conversion member according to any one of [1] to [7], it is preferable that the laminating step is a coating step of a quantum dot-containing composition.
[9] A wavelength conversion member manufactured by the method for manufacturing a wavelength conversion member according to any one of [1] to [8].
[10] A barrier film having at least one inorganic layer subjected to surface treatment;
A wavelength conversion layer containing quantum dots, disposed in direct contact with the surface-treated surface of the barrier film,
The wavelength conversion member whose above-mentioned surface treatment is provision to the surface of the above-mentioned inorganic layer of the above-mentioned barrier film with the composition for surface treatment containing the solvent and organometallic coupling agent containing water.
[11] In the wavelength conversion member according to [9] or [10], the concentration of the organometallic coupling agent in the surface region at a distance of 10% or less in the thickness direction from at least one surface of the wavelength conversion layer described above, The concentration is preferably higher than the concentration of the organometallic coupling agent in the inner region at a distance exceeding 10% in the thickness direction from both surfaces of the wavelength conversion layer.
[12] The wavelength conversion member according to any one of [9] to [11];
A light source;
Including at least a backlight unit.
[13] In the backlight unit according to [12], it is preferable that the above-described light source has an emission center wavelength in a wavelength band of 430 nm to 480 nm.
[14] The backlight unit according to [12] or [13];
A liquid crystal cell;
A liquid crystal display device comprising at least

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the wavelength conversion member in which the adhesiveness after wet heat aging between the wavelength conversion layer containing a quantum dot and a barrier film is favorable can be provided.

1A and 1B are explanatory diagrams of an example of a backlight unit including a wavelength conversion member according to one embodiment of the present invention. FIG. 2 illustrates an example of a liquid crystal display device according to one embodiment of the present invention. FIG. 3 is a schematic configuration diagram of an example of a wavelength conversion member manufacturing apparatus. FIG. 4 is a partially enlarged view of the manufacturing apparatus shown in FIG.

The following description may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. In the present invention and this specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
Further, in the present invention and the present specification, the “half-value width” of a peak refers to the width of the peak at a peak height of ½. Further, light having an emission center wavelength in a wavelength band of 400 to 500 nm, preferably 430 to 480 nm is called blue light, and light having an emission center wavelength in a wavelength band of 500 to 600 nm is called green light. Light having an emission center wavelength in the wavelength band of ˜680 nm is referred to as red light.

[Method for producing wavelength conversion member]
The method for producing a wavelength conversion member of the present invention includes a surface treatment step of surface-treating a barrier film having at least one inorganic layer;
A lamination step of laminating a wavelength conversion layer containing quantum dots on the surface-treated surface of the barrier film,
The surface treatment step is a step of applying a surface treatment composition containing a solvent containing water and an organometallic coupling agent to the surface of the inorganic layer of the barrier film.
With such a configuration, according to the method for manufacturing a wavelength conversion member, it is possible to manufacture a wavelength conversion member having good adhesion after wet heat aging between the wavelength conversion layer containing quantum dots and the barrier film.
Without being bound by any theory, the adhesion between the wavelength conversion layer and the barrier film after wet heat aging is improved by surface-treating the inorganic layer of the barrier film with a composition containing an organometallic coupling agent and water. can do. This is because the organometallic coupling agent with increased reactivity forms a covalent bond with the surface and constituent components of the adjacent barrier film by hydrolysis reaction, condensation reaction, etc. After preparing a composition containing a ring agent and water, surface treatment of the inorganic layer of the barrier film causes the hydrolysis and dehydration condensation of the organometallic coupling agent after laminating the wavelength conversion layer and the barrier film. This is considered to be due to the fact that generation of methanol and water could be suppressed.
Hereinafter, the preferable aspect of the manufacturing method of the wavelength conversion member of this invention is demonstrated.

<Surface treatment process>
The method for producing a wavelength conversion member of the present invention includes a surface treatment step of surface-treating a barrier film having at least one inorganic layer, and the surface treatment step includes a water-containing solvent and an organometallic coupling agent. It is the process of providing the composition for use to the surface of the inorganic layer of a barrier film.

A surface treatment method using a composition for surface treatment containing a solvent containing water and an organometallic coupling agent is not particularly limited, but the surface treatment may be carried out on a barrier film with a roll to roll. From the viewpoint of productivity. Specifically, a method of applying and drying the composition for surface treatment on the barrier film by roll-to-roll using an applicator can be mentioned.
In the method for producing a wavelength conversion member of the present invention, the surface treatment step described above includes a step of surface-treating the first barrier film having at least one inorganic layer and the second barrier film having at least one inorganic layer, respectively. It is preferable that
More preferably, the method for producing a wavelength conversion member of the present invention includes a step of unwinding the first barrier film and the second barrier film, respectively, from a roll before the surface treatment step.

(Barrier film)
The wavelength conversion member includes a barrier film. The barrier film is preferably a film having a gas barrier function of blocking oxygen. It is also preferable that the barrier film has a function of blocking water vapor.
The barrier film is preferably contained in the wavelength conversion member as a layer adjacent to or directly in contact with the wavelength conversion layer. In addition, one or more barrier films may be included in the wavelength conversion member, and the wavelength conversion member has a structure in which a barrier film, a wavelength conversion layer, and a barrier film are laminated in this order. Preferably it is.
In the wavelength conversion member, the wavelength conversion layer may be formed using a barrier film as a base material. The barrier film can also be used for either or both of the first film and the second film described above. When both the first film and the second film are barrier films, they may be the same or different.

The barrier film may be any known barrier film, for example, a barrier film described below.
The barrier film only needs to include at least one inorganic layer, and may be a film including a base film and an inorganic layer. For the base film, the description of the support can be referred to. The barrier film may include a barrier laminate including at least one inorganic layer and at least one organic layer on the base film. Laminating a plurality of layers in this way can further enhance the barrier property, and on the other hand, the light transmittance of the wavelength conversion member tends to decrease as the number of layers to be laminated increases, which is favorable. It is desirable to increase the number of stacked layers as long as a sufficient light transmittance can be maintained. Specifically, the barrier film preferably has a total light transmittance of 80% or more in the visible light region and an oxygen permeability of 1 cm ³ / (m ² · day · atm) or less. Here, the oxygen permeability is a value measured using an oxygen gas permeability measuring device (manufactured by MOCON, OX-TRAN 2/20: trade name) under the conditions of a measurement temperature of 23 ° C. and a relative humidity of 90%. It is. The visible light region means a wavelength region of 380 to 780 nm, and the total light transmittance indicates an average value of light transmittance over the visible light region.
The oxygen permeability of the barrier film is more preferably 0.1 cm ³ / (m ² · day · atm) or less, and more preferably 0.01 cm ³ / (m ² · day · atm) or less. The total light transmittance in the visible light region is more preferably 90% or more. The lower the oxygen permeability, the better, and the higher the total light transmittance in the visible light region, the better.

-Inorganic layer-
The “inorganic layer” is a layer mainly composed of an inorganic material, and is preferably a layer formed only from an inorganic material. On the other hand, the organic layer is a layer mainly composed of an organic material, and preferably refers to a layer in which the organic material occupies 50% by mass or more, more preferably 80% by mass or more, and particularly 90% by mass or more. To do.
The inorganic material constituting the inorganic layer is not particularly limited, and for example, various inorganic compounds such as metals or inorganic oxides, nitrides, oxynitrides, and the like can be used. As an element constituting the inorganic material, silicon, aluminum, magnesium, titanium, tin, indium and cerium are preferable, and one or two or more of these may be included. Specific examples of the inorganic compound include silicon oxide, silicon oxynitride, aluminum oxide, magnesium oxide, titanium oxide, tin oxide, indium oxide alloy, silicon nitride, aluminum nitride, and titanium nitride. As the inorganic layer, a metal film such as an aluminum film, a silver film, a tin film, a chromium film, a nickel film, or a titanium film may be provided.

Among the above materials, silicon-containing compounds such as silicon nitride, silicon oxide, or silicon oxynitride are particularly preferable, and silicon nitride is more particularly preferable. This is because the inorganic layer made of these materials has a good adhesion to the organic layer, and thus the barrier property can be further enhanced.
A method for forming the inorganic layer is not particularly limited, and various film forming methods that can evaporate or scatter the film forming material and deposit it on the deposition surface can be used.

  Examples of the method for forming the inorganic layer include a vacuum evaporation method in which an inorganic material such as an inorganic oxide, an inorganic nitride, an inorganic oxynitride, or a metal is heated and evaporated; an inorganic material is used as a raw material, and oxygen gas is introduced. Oxidation reaction vapor deposition method for oxidizing and vapor-depositing; Sputtering method for vapor deposition by introducing and sputtering argon gas and oxygen gas using an inorganic material as a target raw material; When a vapor deposition film of a compound containing silicon is formed by using a physical vapor deposition method (physical vapor deposition method) such as ion plating, which is heated by a plasma beam and deposited, plasma using an organosilicon compound as a raw material Chemical vapor deposition method (Chemical Vapor Deposition method) etc. And the like. Vapor deposition may be performed on the surface of a substrate, a base film, a wavelength conversion layer, an organic layer, or the like as a substrate.

  The film of the compound containing silicon is preferably formed by using a low temperature plasma chemical vapor deposition method using an organosilicon compound as a raw material. Specific examples of the organosilicon compound include 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, and propyl. Examples thereof include silane, phenylsilane, vinyltriethoxysilane, tetramethoxysilane, phenyltriethoxysilane, methyltriethoxysilane, and octamethylcyclotetrasiloxane. Among the organosilicon compounds, tetramethoxysilane (TMOS) and hexamethyldisiloxane (HMDSO) are preferably used. This is because these are excellent in handleability and vapor deposition film characteristics.

  The thickness of the inorganic layer is, for example, 1 nm to 500 nm, preferably 5 nm to 300 nm, and more preferably 10 nm to 150 nm. When the film thickness of the inorganic layer is within the above-described range, it is possible to suppress reflection in the inorganic layer while realizing good barrier properties, and to provide a wavelength conversion member with higher light transmittance. Because it can.

  The contact angle of the inorganic layer with water is preferably, for example, 5 to 70 °, more preferably 5 to 55 °, and particularly preferably 5 to 35 °. When the contact angle of the inorganic layer with water is within the above-described range, the adhesiveness after wet heat aging between the wavelength conversion layer containing the quantum dots and the barrier film is good, and the barrier film It is easy to provide a wavelength conversion member in which the wavelength conversion layer is uniformly formed on the surface of the inorganic layer without repellency. A lower contact angle of the inorganic layer with water is preferable because of good wettability and coating properties.

  In the manufacturing method of the present invention, the wavelength conversion member includes at least one inorganic layer in direct contact with the wavelength conversion layer. It is also preferable that the inorganic layer is in direct contact with both surfaces of the wavelength conversion layer. However, the inorganic layer generally tends to have difficulty in ensuring adhesion with a wavelength conversion layer formed from a polymerizable composition containing an organic compound. On the other hand, in the wavelength conversion member formed by laminating the wavelength conversion layer containing quantum dots after surface-treating the surface of the inorganic layer of the barrier film with a composition containing an organic metal coupling agent and water, The adhesion after wet heat aging between the inorganic layer of the barrier film and the wavelength conversion layer containing quantum dots is good.

-Organic layer-
JP, 2007-290369, A paragraphs 0020-0042 and JP, 2005-096108, A paragraphs 0074-0105 can be referred to as an organic layer. The organic layer preferably contains a cardo polymer. Thereby, the adhesiveness between the organic layer and the adjacent layer, particularly the adhesiveness with the inorganic layer is improved, and a further excellent gas barrier property can be realized. JP, 2005-096108, A paragraphs 0085-0095 can be referred to for the details of a cardo polymer. The thickness of the organic layer is preferably in the range of 0.05 μm to 10 μm, and more preferably in the range of 0.5 to 10 μm. When the organic layer is formed by a wet coating method, the film thickness of the organic layer is preferably in the range of 0.5 to 10 μm, and more preferably in the range of 1 μm to 5 μm. Moreover, when formed by the dry coating method, it is preferable that it exists in the range of 0.05 micrometer-5 micrometers, especially in the range of 0.05 micrometer-1 micrometer. This is because when the film thickness of the organic layer formed by the wet coating method or the dry coating method is within the above-described range, the adhesion with the inorganic layer can be further improved.

  Regarding other details of the inorganic layer and the organic layer, reference can be made to JP-A-2007-290369, JP-A-2005-096108 and US2012 / 0113672A1.

  A known adhesive layer may be bonded between the organic layer and the inorganic layer, between the two organic layers, or between the two inorganic layers. From the viewpoint of improving light transmittance, it is preferable that the number of adhesive layers is small, and it is more preferable that no adhesive layer is present.

-Other layers and supports-
As described above, the wavelength conversion member has an adjacent layer on at least one main surface of the wavelength conversion layer. For example, at least one main surface of the wavelength conversion layer may have at least one layer selected from the group consisting of an inorganic layer and an organic layer. As such an inorganic layer and an organic layer, the inorganic layer and organic layer which comprise the below-mentioned barrier film can be mentioned. From the viewpoint of maintaining luminous efficiency, it is preferable that both main surfaces of the wavelength conversion layer include at least one layer selected from the group consisting of an inorganic layer and an organic layer. This is because such a layer can prevent invasion of oxygen, moisture, and the like from the main surface into the wavelength conversion layer, and can prevent the quantum dots from being deteriorated and the light emission efficiency from being lowered due to these penetrations. Moreover, in one aspect | mode, it is preferable that an inorganic layer and an organic layer are contained as an adjacent layer which touches the main surface of a wavelength conversion layer directly. In addition, the adhesiveness of the interface of the wavelength conversion layer and the inorganic layer of a barrier film is improved irrespective of an adhesive layer by using a composition for surface treatment containing a solvent containing water and an organometallic coupling agent. Although it does not exclude the use of an adhesive layer. A known adhesive layer may be bonded to the inorganic layer of the barrier film and the wavelength conversion layer.

The wavelength conversion member may have a support for improving strength, easiness of film formation, and the like. The support may be included as a layer adjacent to or directly in contact with the wavelength conversion layer, or may be included as a base film of the barrier film. In the wavelength conversion member, the support may be included so that the inorganic layer described later and the support are in this order, and the wavelength conversion layer, the inorganic layer, the organic layer, and the support are in this order. May be included. A support may be disposed between the organic layer and the inorganic layer, between the two organic layers, or between the two inorganic layers. One or more supports may be included in the wavelength conversion member, and the wavelength conversion member has a structure in which the support, the wavelength conversion layer, and the support are laminated in this order. May be. The support is preferably a transparent support that is transparent to visible light. Here, “transparent to visible light” means that the linear transmittance in the visible light region is 80% or more, preferably 85% or more. The light transmittance used as a measure of transparency is measured by measuring the total light transmittance and the amount of scattered light using the method described in JIS-K7105, that is, using an integrating sphere light transmittance measuring device, and diffusing transmission from the total light transmittance. It can be calculated by subtracting the rate. JP, 2007-290369, A paragraphs 0046-0052 and JP, 2005-096108, A paragraphs 0040-0055 can be referred to for a support. The thickness of the support is preferably in the range of 10 to 500 μm, particularly in the range of 20 to 400 μm, and particularly in the range of 30 to 300 μm, from the viewpoint of gas barrier properties, impact resistance and the like.
The support can also be used as a substrate. Moreover, a support body can also be used for either a 1st film and a 2nd film, or both. When both the first film and the second film are supports, each support may be the same or different.

(Composition for surface treatment)
-Solvent containing water-
The composition for surface treatment contains a solvent containing water. It is preferable that the composition for surface treatment is a solvent of an organometallic coupling agent.
As the surface treatment composition, water is essential in order to accelerate hydrolysis.
In the method for producing a wavelength conversion member of the present invention, the solvent for the surface treatment composition preferably contains an organic solvent in the solvent for the surface treatment composition described above, and the solubility of the organometallic coupling agent is improved. In order to improve, it is preferable to include a polar solvent. Specifically, the polar solvent is preferably an alcohol such as methanol, ethanol or isopropyl alcohol, or a ketone solvent such as acetone or methyl ethyl ketone, more preferably an alcohol, and particularly preferably ethanol or isopropyl alcohol. The mixing ratio of water / polar solvent is preferably 10/90 to 90/10 by mass ratio, more preferably 30/70 to 70/30, still more preferably 40/60 to 60/40. Less water improves the solubility of the organometallic coupling agent. When there is much water, a hydrolysis reaction will be accelerated | stimulated and the adhesive improvement effect will increase.
When the solubility of the organometallic coupling agent in a solvent containing water is insufficient, an acid is preferably added to the solvent of the surface treatment composition for pH adjustment. Specific examples of the acid include acetic acid and boric acid. Acetic acid is more preferred.

-Organometallic coupling agent-
The aforementioned composition for surface treatment contains an organometallic coupling agent such as a silane coupling agent. Of the organometallic coupling agents, silane coupling agents and aluminum coupling agents are preferred, and silane coupling agents are more preferred.
In addition, when the organometallic coupling agent has a reactive functional group such as a radical polymerizable group, the wavelength conversion layer and the inorganic layer may form a crosslinked structure with the polymerizable compound used for forming the wavelength conversion layer. It can be thought that it can contribute to the improvement of adhesion. From this point, it is also preferable to use an organometallic coupling agent having a reactive functional group that has good crosslinking reactivity with the polymerizable compound contained in the composition, and the organometallic coupling agent has a reactive functional group at the end. It is more preferable to have a group. By introducing an organometallic coupling agent having a reactive functional group at the terminal, the present inventors reacted with a polymerizable compound such as an acrylate monomer in the wavelength conversion layer, and improved adhesion after wet heat aging. I guess.
Examples of the reactive functional group that the organometallic coupling agent may have include a vinyl group, an epoxy group, a styryl group, a (meth) acryl group, an amino group, a ureido group, a mercapto group, a sulfide group, and an isocyanate group. be able to.
It is also preferable to improve the adhesion by forming a wavelength conversion layer through a step of adding an acid generator described later to the composition to impart energy for generating a protonic acid. The present inventors speculate that this is because the reaction of the organometallic coupling agent is accelerated by the proton acid generated by the acid generator.

  As the silane coupling agent, a known silane coupling agent can be used without any limitation. Preferred silane coupling agents from the viewpoint of adhesion include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3-glycidoxypropyltrimethoxy. Silane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p- Styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3- Acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl)- 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine and its partial hydrolyzate, 3-trimethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine and its partial hydrolyzate, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyl Trimethoxysilane, 3-isocyanate pro Such as Le triethoxy silane. Of these, vinyl, epoxy, (meth) acryloyloxy, amino, and isocyanate-modified silane coupling agents are preferable, and (meth) acryloyloxy-modified silane coupling agents are particularly preferable. As these silane coupling agents, for example, those from Shin-Etsu Chemical Co., Ltd. can be used.

  Moreover, as a silane coupling agent, the silane coupling agent represented by General formula (1) as described in Unexamined-Japanese-Patent No. 2013-43382 can be mentioned. For details, the description of Unexamined-Japanese-Patent No. 2013-43382 Paragraphs 0011-0016 can be referred.

  As other organometallic coupling agents, for example, various coupling agents such as a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, and a tin coupling agent can be used.

  Examples of titanium coupling agents include isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) Titanate, tetra (2,2-diallyloxymethyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl Titanate, isopropyl isostearoyl diacryl titanate, isop Pirutori (dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, isopropyl tri (N- aminoethyl-aminoethyl) titanate, dicumyl phenyloxy acetate titanate, diisostearoyl ethylene titanate.

  Examples of the zirconium coupling agent include tetra-n-propoxyzirconium, tetra-butoxyzirconium, zirconium tetraacetylacetonate, zirconium dibutoxybis (acetylacetonate), zirconium tributoxyethyl acetoacetate, zirconium butoxyacetylacetonate bis. (Ethyl acetoacetate) and the like.

  Examples of the aluminum coupling agent include aluminum isopropylate, monosec-butoxyaluminum diisopropylate, aluminum sec-butyrate, aluminum ethylate, ethylacetoacetate aluminum diisopropylate, aluminum tris (ethylacetoacetate), alkylacetate Acetate aluminum diisopropylate, aluminum monoacetylacetonate bis (ethyl acetoacetate), aluminum tris (acetylacetoacetate) and the like can be mentioned.

  From the viewpoint of further improving the adhesion between the inorganic layer of the barrier film and the wavelength conversion layer, the organometallic coupling agent may be contained in the surface treatment composition in an amount of 1 to 80% by mass. More preferably, it is 10-70 mass%, More preferably, it is 20-60 mass%.

-Surfactant-
In the method for producing a wavelength conversion member of the present invention, the surface treatment composition preferably contains a surfactant. When using a solution containing an organic metal coupling agent in water as a surface treatment composition, the surface treatment composition has surface activity from the viewpoint of improving the wettability of the hydrophobic barrier film with the inorganic layer surface. It is preferable to reduce the surface tension by adding an agent.
As the surfactant in the present invention, any of an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant can be used. Furthermore, a surfactant containing fluorine is particularly preferable.
Specific examples of anionic surfactants include, for example, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium alkyldiphenyl ether disulfonate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate, sodium stearate, potassium oleate, sodium dioctyl Sulfosuccinate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate, sodium dialkylsulfosuccinate, sodium stearate, sodium oleate, t-octylphenoxyethoxypolyethoxyethyl Examples include sodium sulfate, etc., and select one or more of these Rukoto can.
Specific examples of the nonionic surfactant include, for example, polyoxyethylene lauryl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene oleyl phenyl ether, polyoxyethylene nonyl phenyl ether, oxyethylene / oxypropylene block copolymer, t- Examples include octylphenoxyethyl polyethoxyethanol, nonylphenoxyethyl polyethoxyethanol, and the like, and one or more of these can be selected.
Examples of the cationic surfactant include tetraalkylammonium salts, alkylamine salts, benzalkonium salts, alkylpyridium salts, imidazolium salts, and the like. Specific examples thereof include dihydroxyethyl stearylamine and 2-heptadecenyl. -Hydroxyethylimidazoline, lauryltrimethylbenzylammonium chloride, cetylpyridinium chloride, stearamide methylpyridium chloride and the like.
As the surfactant containing fluorine, as an anionic surfactant, F-114 F-410 manufactured by DIC, and as a nonionic surfactant, F-444, F-553, F-556, F-559, F-567, F-569, R-94, etc. are mentioned.
In the method for producing a wavelength conversion member of the present invention, the aforementioned surfactant is preferably a fluorine-based nonionic surfactant.

-Reaction accelerator-
The composition for surface treatment may contain a reaction accelerator together with the components described above. A reaction accelerator means a compound that promotes an organometallic coupling reaction. Examples of the reaction accelerator include an acid generator. Examples of the acid generator include an acid generator that generates a protonic acid by applying energy. The composition for surface treatment may contain an acid generator that generates a protonic acid by applying energy. Such an acid generator is usually an ionic compound or salt containing an anion portion X ⁻ and a cation portion Y ⁺ , which decomposes upon application of energy to extract proton H ⁺ from the solvent or the acid generator itself. Protic acid XH can be generated. Here, the protonic acid refers to a compound capable of releasing proton H ⁺ .

  The energy application method for generating the protonic acid from the acid generator is not particularly limited, and examples thereof include light irradiation, heat treatment, irradiation with active energy rays such as radiation and electromagnetic waves. Preferably, light irradiation and heat treatment are performed. That is, the acid generator is preferably selected from the group consisting of a photoacid generator and a thermal acid generator. The light irradiated to give energy to the photoacid generator is, for example, ultraviolet light. However, if the acid generator included in the composition can perform light irradiation capable of generating a proton acid, the light to be irradiated The wavelength of is not limited. The energy application conditions such as the light irradiation conditions and the heating conditions are not particularly limited as long as the acid generator contained in the composition can generate a protonic acid.

Examples of the photoacid generator include diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, onium salts such as arsonium salts, organic halogen compounds, organic metal / organic halides, and o-nitrobenzyl type. A photoacid generator having a protecting group, a compound capable of generating sulfonic acid by photolysis, such as iminosulfonate, a disulfone compound, a diazoketosulfone, a diazodisulfone compound, and the like. Further, triazines, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds can also be mentioned.
Further, a group that generates an acid by light, or a compound in which a compound is introduced into the main chain or side chain of a polymer can be used.

  Furthermore, V. N. R. Pillai, Synthesis, (1), 1 (1980), A.M. Abad et al. , Tetrahedron Lett. , (47) 4555 (1971), D.M. H. R. Barton et al. , J. et al. Chem. Soc. , (C), 329 (1970), U.S. Pat. No. 3,779,778, European Patent 126,712 and the like, compounds that generate an acid by light can also be used.

  Specific examples of the photoacid generator include photoacid generators <A-1> to <A-4> described in [0076] to [0102] of JP-A-2008-162952. .

Examples of the thermal acid generator include salts composed of an acid and an organic base.
Examples of the acid include organic acids such as sulfonic acid, phosphonic acid, and carboxylic acid, and inorganic acids such as sulfuric acid and phosphoric acid. From the viewpoint of compatibility with the matrix, organic acids are more preferred, sulfonic acids and phosphonic acids are more preferred, and sulfonic acids are most preferred. Preferred sulfonic acids include p-toluenesulfonic acid (PTS), benzenesulfonic acid (BS), p-dodecylbenzenesulfonic acid (DBS), p-chlorobenzenesulfonic acid (CBS), 1,4-naphthalenedisulfonic acid (NDS). ), Methanesulfonic acid (MsOH), nonafluorobutane-1-sulfonic acid (NFBS), and the like, and any of them can be preferably used (the abbreviations in () are used).

  About the basicity of the organic base which forms a salt with an acid, when expressed using pKa of a conjugate acid, pKa is preferably 5.0 to 10.5, and preferably 6.0 to 10.0. More preferably, it is 6.5-10.0. The value of pKa of organic base in aqueous solution is described in Chemistry Handbook Basic Edition (5th revised edition, edited by The Chemical Society of Japan, Maruzen, 2004) Volume II, pages II-334-340. An organic base having an appropriate pKa can be selected. In addition, a compound that can be presumed to have a pKa that is structurally appropriate even if not described in the above-mentioned document can be preferably used. The compounds having appropriate pKa described in the above-mentioned literature are shown in Table 1 below, but the present invention is not limited thereto.

  On the other hand, the lower the boiling point of the organic base, the higher the acid generation efficiency during heating, which is preferable from the viewpoint of promoting the reaction of the organometallic coupling agent. Therefore, it is preferable to use an organic base having an appropriate boiling point. The boiling point of the organic base is preferably 120 ° C. or lower, more preferably 80 ° C. or lower, and further preferably 70 ° C. or lower.

Specific examples of the thermal acid generator include the following compounds, but are not limited thereto. Figures in parentheses indicate boiling points.
b-3: pyridine (115 ° C), b-14: 4-methylmorpholine (115 ° C), b-20: diallylmethylamine (111 ° C), b-19: triethylamine (88.8 ° C), b-21 : T-butylmethylamine (67-69 ° C), b-22: dimethylisopropylamine (66 ° C), b-23: diethylmethylamine (63-65 ° C), b-24: dimethylethylamine (36-38 ° C) ).
The boiling point of the organic base is preferably 35 ° C. or higher and 120 ° C. or lower, and more preferably 40 ° C. or higher and 115 ° C. or lower.

  The thermal acid generator may be used by isolating a salt composed of an acid and an organic base, or by mixing the acid and the organic base to form a salt in the solution, and using the solution. Moreover, only one kind of acid or organic base may be used, or a plurality of kinds may be mixed and used. When an acid and an organic base are mixed and used, it is preferable that the acid and the organic base have an equivalent ratio of 1: 0.9 to 1.5, preferably 1: 0.95 to 1.3. It is more preferable to mix in a ratio of 1: 1.0 to 1.1.

  The molecular weight of the protonic acid (the aforementioned XH) generated by applying energy to the acid generator is not particularly limited. It is considered that the reaction of the organometallic coupling agent is promoted by the generated proton acid. However, the progress of this reaction at the interface with the adjacent layer improves the adhesion at the interface between the wavelength conversion layer and the adjacent layer. It is preferable for this purpose. For this purpose, the present inventors presume that the generated proton acid preferably has a relatively low molecular weight and good mobility in the wavelength conversion layer. From this point, what is the molecular weight of the generated protonic acid? Preferably it is 500 or less, More preferably, it is 300 or less, More preferably, it is 200 or less, More preferably, it is 100 or less. The lower limit of the molecular weight is, for example, 30 or more, but is not particularly limited.

  The acid generator demonstrated above is 0.01-30 mass parts with respect to the said composition, for example with respect to 100 mass parts of said polymeric compounds whole quantity, Preferably it is 0.1-20 mass parts, More preferably, 0.5- 5 parts by mass can be included.

<Lamination process>
The manufacturing method of the wavelength conversion member of this invention includes the lamination process which laminates | stacks the wavelength conversion layer containing a quantum dot on the surface by which the surface treatment of the barrier film was carried out.

In the method for producing a wavelength conversion member of the present invention, it is preferable that the laminating step is a coating step of a quantum dot-containing composition. The quantum dot-containing composition is a quantum dot-containing polymerizable composition, and it is more preferable that the quantum dot-containing polymerizable composition after coating is polymerized (cured). In the following, although a quantum dot-containing polymerizable composition may be described as a representative example of a description of a preferred embodiment of a lamination step using a quantum dot-containing composition, a preferred embodiment of a lamination step using a quantum dot-containing composition Is not limited to a quantum dot-containing polymerizable composition.
Application methods of the quantum dot-containing composition include curtain coating method, dip coating method, spin coating method, print coating method, spray coating method, slot coating method, roll coating method, slide coating method, blade coating method, and gravure coating. And a known coating method such as a wire bar method.
The curing conditions can be appropriately set according to the type of polymerizable compound used and the composition of the polymerizable composition. Moreover, when a quantum dot containing polymeric composition is a composition containing a solvent, you may perform a drying process for solvent removal, before performing a polymerization process.

The wavelength conversion layer is preferably a layer formed by subjecting the quantum dot-containing polymerizable composition to a polymerization treatment. The polymerization treatment of the quantum dot-containing polymerizable composition can be performed by light irradiation or heating.
When the composition for surface treatment contains a reaction accelerator such as an acid generator, the method of polymerizing the quantum dot-containing polymerizable composition and the method for imparting energy to the acid generator of the composition for surface treatment are particularly limited. Not. For example, in an embodiment in which the acid generator is a photoacid generator and the polymerization treatment of the polymerizable composition is performed by light irradiation, the energy application and the polymerization treatment can be performed simultaneously, that is, as one step. The same applies to the aspect in which the acid generator is a thermal acid generator and the polymerization treatment is performed by heating. On the other hand, in an embodiment in which the acid generator is a thermal acid generator and the polymerization treatment is performed by light irradiation, energy application (heating) and polymerization treatment (light irradiation) are sequentially performed as separate steps. The same applies to the aspect in which the acid generator is a photoacid generator and the polymerization treatment is performed by heating. Thus, when energy provision and a polymerization process are performed by a separate process, it is preferable to perform a polymerization process after performing energy provision. This is because it is considered that performing the polymerization treatment after promoting the reaction of the organometallic coupling agent by applying energy contributes to further improving the adhesion between the wavelength conversion layer and the inorganic layer. For the same reason, energy application and polymerization treatment are both performed by light irradiation, and the light irradiation conditions for energy application (for example, the wavelength of light to be irradiated) are different from those of the polymerization treatment. It is preferable to perform light irradiation for polymerization treatment after light irradiation for energy application. This is the case where both the energy application and the polymerization process are performed by heating, and the same applies when the heating conditions for energy application and the heating conditions for the polymerization process are different.

In the wavelength conversion member manufacturing method of the present invention, the laminating step is a step of sandwiching the wavelength conversion layer between the surface-treated surfaces of the first barrier film and the second barrier film, respectively. However, it is more preferable from the viewpoint of improving the barrier property of the wavelength conversion member.
In one aspect of the method for producing a wavelength conversion member of the present invention, the polymerization treatment of the quantum dot-containing polymerizable composition can be performed in a state where the composition is sandwiched between two substrates. One aspect of the manufacturing process of the wavelength conversion member including such a polymerization process will be described below with reference to the drawings. However, the present invention is not limited to the following embodiments.

FIG. 3 is a schematic configuration diagram of an example of the wavelength conversion member manufacturing apparatus 100, and FIG. 4 is a partial enlarged view of the manufacturing apparatus shown in FIG. The manufacturing process of the wavelength conversion member using the manufacturing apparatus 100 shown in FIGS.
Applying a quantum dot-containing polymerizable composition to the surface of a first substrate (hereinafter also referred to as “first film”) that is continuously conveyed to form a coating film;
A second substrate (hereinafter also referred to as “second film”) that is continuously conveyed is laminated (overlapped) on the coating film, and the first film and the second film are coated. A process of sandwiching
In a state where the coating film is sandwiched between the first film and the second film, either the first film or the second film is wound around a backup roller and irradiated with light while being continuously conveyed. A step of polymerizing and curing to form a wavelength conversion layer (cured layer);
Is an embodiment of the production method of the present invention including at least By using a barrier film having an inorganic layer (preferably an inorganic layer having a barrier property against oxygen and moisture) as either the first base material or the second base material, one side is a barrier film (barrier layer). A protected wavelength conversion member can be obtained. Moreover, the wavelength conversion member by which the both surfaces of the wavelength conversion layer were protected by the barrier film (barrier layer) can be obtained by using a barrier film as a 1st base material and a 2nd base material, respectively.

  More specifically, first, the first film 10 is continuously conveyed to the coating unit 20 from a delivery machine (not shown). For example, the first film 10 is sent out from the sending machine at a conveying speed of 1 to 50 m / min. However, it is not limited to this conveyance speed. When delivered, for example, a tension of 20 to 150 N / m, preferably 30 to 100 N / m, is applied to the first film 10.

  In the coating unit 20, a quantum dot-containing polymerizable composition (hereinafter also referred to as “coating liquid”) is applied to the surface of the first film 10 that is continuously conveyed, and a coating film 22 (see FIG. 2) is formed. Is done. In the coating unit 20, for example, a die coater 24 and a backup roller 26 disposed to face the die coater 24 are installed. The surface of the first film 10 opposite to the surface on which the coating film 22 is formed is wound around the backup roller 26, and the coating liquid is applied from the discharge port of the die coater 24 onto the surface of the first film 10 that is continuously conveyed. As a result, the coating film 22 is formed. Here, the coating film 22 refers to a quantum dot-containing composition before the polymerization treatment applied on the first film 10.

  In the present embodiment, the die coater 24 to which the extrusion coating method is applied is shown as the coating apparatus, but the present invention is not limited to this. For example, a coating apparatus to which various methods such as a curtain coating method, an extrusion coating method, a rod coating method, or a roll coating method are applied can be used.

  The first film 10 that has passed through the coating unit 20 and has the coating film 22 formed thereon is continuously conveyed to the laminating unit 30. In the laminating unit 30, the second film 50 that is continuously conveyed is laminated on the coating film 22, and the coating film 22 is sandwiched between the first film 10 and the second film 50.

  The laminating unit 30 is provided with a laminating roller 32 and a heating chamber 34 surrounding the laminating roller 32. The heating chamber 34 is provided with an opening 36 for allowing the first film 10 to pass therethrough and an opening 38 for allowing the second film 50 to pass therethrough.

  A backup roller 62 is disposed at a position facing the laminating roller 32. The first film 10 on which the coating film 22 is formed is wound around the backup roller 62 on the surface opposite to the surface on which the coating film 22 is formed, and is continuously conveyed to the laminating position P. The laminating position P means a position where the contact between the second film 50 and the coating film 22 starts. The first film 10 is preferably wound around the backup roller 62 before reaching the laminating position P. This is because even if wrinkles occur in the first film 10, the wrinkles are corrected by the backup roller 62 before reaching the laminate position P and can be removed. Accordingly, the position where the first film 10 is wound around the backup roller 62 (contact position) and the distance L1 to the laminating position P are preferably longer, for example, 30 mm or more is preferable, and the upper limit is usually It is determined by the diameter of the backup roller 62 and the pass line.

  In the present embodiment, the second film 50 is laminated by the backup roller 62 and the laminating roller 32 used in the polymerization processing unit 60. That is, the backup roller 62 used in the polymerization processing unit 60 is also used as a roller used in the laminating unit 30. However, the present invention is not limited to the above form, and a laminating roller may be installed in the laminating unit 30 in addition to the backup roller 62 so that the backup roller 62 is not used.

  By using the backup roller 62 used in the polymerization processing unit 60 in the laminating unit 30, the number of rollers can be reduced. The backup roller 62 can also be used as a heat roller for the first film 10.

  The second film 50 delivered from a delivery machine (not shown) is wound around the laminating roller 32 and continuously conveyed between the laminating roller 32 and the backup roller 62. The second film 50 is laminated on the coating film 22 formed on the first film 10 at the laminating position P. Accordingly, the coating film 22 is sandwiched between the first film 10 and the second film 50. Lamination refers to laminating the second film 50 on the coating film 22.

  The distance L2 between the laminating roller 32 and the backup roller 62 is a value of the total thickness of the first film 10, the wavelength conversion layer (cured layer) 28 obtained by polymerizing and curing the coating film 22, and the second film 50. The above is preferable. Moreover, it is preferable that L2 is below the length which added 5 mm to the total thickness of the 1st film 10, the coating film 22, and the 2nd film 50. FIG. By setting the distance L2 to be equal to or shorter than the total thickness plus 5 mm, it is possible to prevent bubbles from entering between the second film 50 and the coating film 22. Here, the distance L <b> 2 between the laminating roller 32 and the backup roller 62 refers to the shortest distance between the outer peripheral surface of the laminating roller 32 and the outer peripheral surface of the backup roller 62.

  The rotational accuracy of the laminating roller 32 and the backup roller 62 is 0.05 mm or less, preferably 0.01 mm or less in radial runout. The smaller the radial runout, the smaller the thickness distribution of the coating film 22.

  Further, in order to suppress thermal deformation after the coating film 22 is sandwiched between the first film 10 and the second film 50, the temperature of the backup roller 62 of the polymerization processing unit 60 and the temperature of the first film 10 are The difference and the difference between the temperature of the backup roller 62 and the temperature of the second film 50 are preferably 30 ° C. or less, more preferably 15 ° C. or less, and most preferably the same.

  In order to reduce the difference from the temperature of the backup roller 62, when the heating chamber 34 is provided, it is preferable to heat the first film 10 and the second film 50 in the heating chamber 34. For example, hot air is supplied to the heating chamber 34 by a hot air generator (not shown), and the first film 10 and the second film 50 can be heated.

  The first film 10 may be heated by the backup roller 62 by being wound around the temperature-adjusted backup roller 62.

On the other hand, the second film 50 can be heated by the laminating roller 32 by using the laminating roller 32 as a heat roller.
However, the heating chamber 34 and the heat roller are not essential and can be provided as necessary.

  Next, the film 22 is continuously conveyed to the polymerization processing unit 60 in a state where the coating film 22 is sandwiched between the first film 10 and the second film 50. In the embodiment shown in the drawing, the polymerization treatment in the polymerization treatment unit 60 is performed by light irradiation, but when the polymerizable compound contained in the quantum dot-containing polymerizable composition is polymerized by heating, spraying hot air is performed. The polymerization treatment can be performed by heating such as. In addition, when the energy application is performed in one step with the polymerization process, the polymerization process unit 60 performs the energy application. On the other hand, when the energy application and the polymerization process are performed in separate steps, it is preferable to perform the energy application before the polymerization process for the reason described above.

A light irradiation device 64 is provided at a position facing the backup roller 62 and the backup roller 62. The first film 10 and the second film 50 sandwiching the coating film 22 are continuously conveyed between the backup roller 62 and the light irradiation device 64. What is necessary is just to determine the light irradiated by a light irradiation apparatus according to the kind of photopolymerizable compound contained in a quantum dot containing polymeric composition, and an ultraviolet-ray is mentioned as an example. Here, the ultraviolet light refers to light having a wavelength of 280 to 400 nm. As a light source that generates ultraviolet rays, for example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. What is necessary is just to set the light irradiation amount to the range which can advance the polymerization hardening of a coating film, for example, the ultraviolet-ray of the irradiation amount of 100-10000mJ / cm < ² > can be irradiated toward the coating film 22 as an example.

  In the polymerization processing unit 60, the first film 10 and the second film 50 sandwich the coating film 22, the first film 10 is wound around the backup roller 62, and the light irradiation device 64 is continuously conveyed. The wavelength conversion layer (cured layer) 28 can be formed by irradiating with light and curing the coating film 22.

  In the present embodiment, the first film 10 side is wound around the backup roller 62 and continuously conveyed, but the second film 50 may be wound around the backup roller 62 and continuously conveyed.

  Wrapping around the backup roller 62 means a state in which either the first film 10 or the second film 50 is in contact with the surface of the backup roller 62 at a certain wrap angle. Accordingly, the first film 10 and the second film 50 move in synchronization with the rotation of the backup roller 62 while being continuously conveyed. Wrapping around the backup roller 62 may be at least during the irradiation of ultraviolet rays.

  The backup roller 62 includes a cylindrical body and rotation shafts disposed at both ends of the body. The main body of the backup roller 62 has a diameter of φ200 to 1000 mm, for example. There is no restriction on the diameter φ of the backup roller 62. In consideration of curl deformation of the laminated film, equipment cost, and rotation accuracy, the diameter is preferably 300 to 500 mm. The temperature of the backup roller 62 can be adjusted by attaching a temperature controller to the main body of the backup roller 62.

  The temperature of the backup roller 62 takes into consideration the heat generation during light irradiation, the curing efficiency of the coating film 22, and the occurrence of wrinkle deformation on the backup roller 62 of the first film 10 and the second film 50. Can be determined. For example, the backup roller 62 is preferably set to a temperature range of 10 to 95 ° C, and more preferably 15 to 85 ° C. Here, the temperature related to the roller refers to the surface temperature of the roller.

  A distance L3 between the laminate position P and the light irradiation device 64 can be set to, for example, 30 mm or more.

  The coating film 22 becomes the cured layer 28 by light irradiation, and the wavelength conversion member 70 including the first film 10, the cured layer 28, and the second film 50 is manufactured. The wavelength conversion member 70 is peeled from the backup roller 62 by the peeling roller 80. The wavelength conversion member 70 is continuously conveyed to a winder (not shown), and then the wavelength conversion member 70 is wound into a roll by the winder.

  As mentioned above, although the one aspect | mode of the manufacturing process of the wavelength conversion member was demonstrated, this invention is not limited to the said aspect. For example, a wavelength conversion layer (cured by applying a polymerization treatment after applying a drying treatment as necessary without applying a quantum dot-containing composition on a substrate and laminating a further substrate thereon. Layer) may be produced. One or more other layers such as a barrier layer can be laminated on the prepared wavelength conversion layer by a known method.

  The total thickness of the wavelength conversion layer is preferably in the range of 1 to 500 μm, more preferably in the range of 100 to 400 μm. Further, the wavelength conversion layer may have a laminated structure of two or more layers, and may contain quantum dots showing two or more different light emission characteristics in the same layer. When the wavelength conversion layer is a laminate of two or more layers, the thickness of one layer is preferably in the range of 1 to 300 μm, more preferably in the range of 10 to 250 μm, and still more preferably 30 to The range is 150 μm.

(Quantum dot-containing composition)
The quantum dot-containing composition includes quantum dots that are excited by excitation light and emit fluorescence.
The wavelength conversion layer can be formed from the quantum dot-containing composition by, for example, a coating method. The quantum dot-containing composition is preferably a quantum dot-containing polymerizable composition further containing a polymerizable compound. When the quantum dot-containing polymerizable composition is used, specifically, the wavelength is obtained by applying the quantum dot-containing polymerizable composition (curable composition) onto a substrate and then performing a curing treatment by light irradiation or the like. A conversion layer can be obtained.
Hereinafter, the quantum dot-containing composition will be described in more detail.

-Quantum dots-
The quantum dot-containing composition contains at least one kind of quantum dot, and can also contain two or more kinds of quantum dots having different emission characteristics. The known quantum dots include a quantum dot A having an emission center wavelength in the wavelength band of 600 nm to 680 nm, a quantum dot B having an emission center wavelength in the wavelength band of 500 nm to 600 nm, and a wavelength band of 400 nm to 500 nm. There is a quantum dot C having an emission center wavelength. The quantum dots A are excited by excitation light to emit red light, the quantum dots B emit green light, and the quantum dots C emit blue light. For example, when blue light is incident as excitation light on a wavelength conversion layer including quantum dots A and B, red light emitted from quantum dots A, green light emitted from quantum dots B, and wavelength conversion layers White light can be realized by the transmitted blue light. Alternatively, by making ultraviolet light as excitation light incident on a wavelength conversion layer including quantum dots A, B, and C, red light emitted by quantum dots A, green light emitted by quantum dots B, and quantum dots White light can be realized by blue light emitted by C. As the quantum dots, those prepared by known methods and commercially available products can be used without any limitation. As for the quantum dots, for example, paragraphs 0060 to 0066 of JP2012-169271A can be referred to, but the quantum dots are not limited thereto. The emission wavelength of the quantum dots can usually be adjusted by the composition and size of the particles, and the composition and size.

  The quantum dots may be mixed in the form of particles with other components at the time of preparing the quantum dot-containing composition, or may be mixed in the state of a dispersion dispersed in a solvent. The addition in the state of a dispersion is preferable from the viewpoint of suppressing the aggregation of the quantum dot particles. The solvent used here is not particularly limited. A quantum dot can be added about 0.01-10 mass parts with respect to 100 mass parts of whole quantity of a quantum dot containing composition, for example.

A specific mode of wavelength conversion in the wavelength conversion member including the above quantum dots will be described below with reference to the drawings. However, the present invention is not limited to the following specific embodiments.
FIG. 1 is an explanatory diagram of an example of a backlight unit 1 including a wavelength conversion member according to an aspect of the present invention. In FIG. 1, the backlight unit 1 includes a light source 1A and a light guide plate 1B for making a surface light source. In the example shown in FIG. 1A, the wavelength conversion member is disposed on the path of light emitted from the light guide plate. On the other hand, in the example shown in FIG. 1B, the wavelength conversion member is disposed between the light guide plate and the light source.
And in the example shown to Fig.1 (a), the light radiate | emitted from the light-guide plate 1B injects into the wavelength conversion member 1C. In the example shown in FIG. 1A, the light 2 emitted from the light source 1A disposed at the edge portion of the light guide plate 1B is blue light, and the liquid crystal is applied from the surface on the liquid crystal cell (not shown) side of the light guide plate 1B. It is emitted toward the cell. The wavelength conversion member 1C disposed on the path of light (blue light 2) emitted from the light guide plate 1B is excited by the blue light 2 and the quantum dots A that are excited by the blue light 2 and emit the red light 4. At least a quantum dot B that emits green light 3 is included. In this way, the backlight unit 1 emits the excited green light 3 and red light 4 and the blue light 2 transmitted through the wavelength conversion member 1C. By emitting RGB light in this way, white light can be realized.
The example shown in FIG. 1B is the same as the embodiment shown in FIG. 1A except that the arrangement of the wavelength conversion member and the light guide plate is different. In the example shown in FIG. 1B, the excited green light 3 and red light 4 and the blue light 2 transmitted through the wavelength conversion member 1C are emitted from the wavelength conversion member 1C and enter the light guide plate, and the surface light source is Realized.

-Polymerizable compound-
In the wavelength conversion layer formed using the quantum dot-containing polymerizable composition as the quantum dot-containing composition, the quantum dots are included in a matrix (polymer) obtained by polymerizing a polymerizable compound by light irradiation or the like. Is preferred.
The shape of the wavelength conversion layer is not particularly limited. For example, the wavelength conversion layer and the wavelength conversion member including this layer are in the form of a sheet or film.

  As the polymerizable compound, polymerizable compounds in various polymerization formats such as radically polymerizable compounds, cationically polymerizable compounds, and anionic polymerizable compounds can be used. Moreover, a polymeric compound may be used individually and may be used in mixture of 2 or more types. The content of the polymerizable compound in the total amount of the composition is preferably about 10 to 99.99% by mass. As an example of a preferable polymerizable compound, monofunctional or polyfunctional (monofunctional or polyfunctional (meth) acrylate monomer, its polymer, prepolymer, etc.) from the viewpoint of transparency and adhesion of the cured film after curing. Mention may be made of (meth) acrylate compounds. In addition, in this invention and this specification, description with "(meth) acrylate" shall be used by the meaning of at least one of an acrylate and a methacrylate, or either. The same applies to “(meth) acryloyl” and the like.

Monofunctional (meth) acrylate compounds include acrylic acid and methacrylic acid, derivatives thereof, and more specifically, compounds having one polymerizable unsaturated bond ((meth) acryloyl group) of (meth) acrylic acid in the molecule Can be mentioned. Specific examples thereof include the following compounds, but the present invention is not limited thereto.
Methyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, stearyl ( Alkyl (meth) acrylates having an alkyl group such as meth) acrylate having 1 to 30 carbon atoms; aralkyl (meth) acrylates having an aralkyl group such as benzyl (meth) acrylate having 7 to 20 carbon atoms; butoxyethyl (meta) ) An alkoxyalkyl (meth) acrylate having 2-30 carbon atoms of an alkoxyalkyl group such as acrylate; the total carbon number of a (monoalkyl or dialkyl) aminoalkyl group such as N, N-dimethylaminoethyl (meth) acrylate; 1-2 An aminoalkyl (meth) acrylate which is: (meth) acrylate of diethylene glycol ethyl ether, (meth) acrylate of triethylene glycol butyl ether, (meth) acrylate of tetraethylene glycol monomethyl ether, (meth) acrylate of hexaethylene glycol monomethyl ether, Octaethylene glycol monomethyl ether (meth) acrylate, nonaethylene glycol monomethyl ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, heptapropylene glycol monomethyl ether (meth) acrylate, tetraethylene glycol monoethyl Alkylene chain such as ether (meth) acrylate has 1-10 carbon atoms and terminal alkyl (Meth) acrylate of polyalkylene glycol alkyl ether having 1 to 10 carbon atoms of ether; alkylene chain such as (meth) acrylate of hexaethylene glycol phenyl ether having 1 to 30 carbon atoms and terminal aryl ether having 6 carbon atoms (Meth) acrylate of -20 polyalkylene glycol aryl ethers; alicyclic structures such as cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, and methylene oxide-added cyclodecatriene (meth) acrylate (Meth) acrylate having 4 to 30 carbon atoms in total; fluorinated alkyl (meth) acrylate having 4 to 30 carbon atoms in total such as heptadecafluorodecyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, mono (meth) acrylate of triethylene glycol, tetraethylene glycol mono (meth) acrylate, hexaethylene glycol mono (meth) acrylate, octapropylene glycol mono (Meth) acrylate, (meth) acrylate having a hydroxyl group such as glycerol mono- or di (meth) acrylate; (meth) acrylate having a glycidyl group such as glycidyl (meth) acrylate; tetraethylene glycol mono (meth) acrylate, hexa Polyethylene glycol mono (methyl) having 1 to 30 carbon atoms in the alkylene chain such as ethylene glycol mono (meth) acrylate and octapropylene glycol mono (meth) acrylate. ) Acrylate; (meth) acrylamide, N, N- dimethyl (meth) acrylamide, N- isopropyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide, acryloyl morpholine (meth) acrylamide and the like.

  As a monofunctional (meth) acrylate compound, it is preferable to use an alkyl (meth) acrylate having 4 to 30 carbon atoms, and using an alkyl (meth) acrylate having 12 to 22 carbon atoms can improve the dispersibility of quantum dots. From the viewpoint of, it is more preferable. As the dispersibility of the quantum dots improves, the amount of light that goes straight from the wavelength conversion layer to the exit surface increases, which is effective in improving front luminance and front contrast. Specifically, as monofunctional (meth) acrylate compounds, butyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, oleyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate Butyl (meth) acrylamide, octyl (meth) acrylamide, lauryl (meth) acrylamide, oleyl (meth) acrylamide, stearyl (meth) acrylamide, behenyl (meth) acrylamide and the like are preferable. Of these, lauryl (meth) acrylate, oleyl (meth) acrylate, and stearyl (meth) acrylate are particularly preferable.

Polyfunctional (meth) acrylate compound having two or more (meth) acryloyl groups in the molecule together with a monomer having one polymerizable unsaturated bond ((meth) acryloyl group) in one molecule. Can also be used together. Specific examples include the following compounds, but the present invention is not limited thereto.
Alkylene glycol di having 1 to 20 carbon atoms in the alkylene chain, such as 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate (Meth) acrylate; polyalkylene glycol di (meth) acrylate having 1 to 20 carbon atoms in the alkylene chain such as polyethylene glycol di (meth) acrylate and polypropylene glycol di (meth) acrylate; trimethylolpropane tri (meth) acrylate, Tri (meth) acrylate having a total carbon number of 10-60, such as ethylene oxide-added trimethylolpropane tri (meth) acrylate; ethylene oxide-added pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) Acrylate, the total number of carbon atoms such as pentaerythritol tetra (meth) acrylate is 10 to 100 of the tetra (meth) acrylate; and the like dipentaerythritol hexa (meth) acrylate.

  The amount of the polyfunctional (meth) acrylate compound such as bifunctional or trifunctional is 5 parts by mass or more from the viewpoint of coating film strength with respect to 100 parts by mass of the total amount of the polymerizable compound contained in the polymerizable composition. From the viewpoint of suppressing the gelation of the composition, it is preferably 95 parts by mass or less. From the same viewpoint, the amount of the monofunctional (meth) acrylate compound used is 5 parts by mass or more and 95 parts by mass or less with respect to 100 parts by mass of the total amount of the polymerizable compounds contained in the polymerizable composition. It is preferable.

  Preferred examples of the polymerizable compound include compounds having a cyclic group such as a cyclic ether group capable of ring-opening polymerization such as an epoxy group and an oxetanyl group. More preferable examples of such a compound include compounds having an epoxy group-containing compound (epoxy compound).

  Examples of the epoxy compound include aliphatic cyclic epoxy compounds, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, and brominated bisphenol. S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin Triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol Diglycidyl ethers; polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin; aliphatic long-chain dibases Diglycidyl esters of acids; monoglycidyl ethers of aliphatic higher alcohols; monoglycidyl ethers of polyether alcohols obtained by adding phenol, cresol, butylphenol or alkylene oxide to these; glycidyl esters of higher fatty acids, etc. It can be illustrated.

  Epoxy compounds further include polyglycidyl esters of polybasic acids, polyglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of polyoxyalkylene glycols, polyglycidyl ethers of aromatic polyols, and polyphenols of aromatic polyols. Mention may also be made of hydrogenated compounds of glycidyl ethers, urethane polyepoxy compounds and epoxidized polybutadienes.

  Among these components, aliphatic cyclic epoxy compounds, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether are preferred.

  Commercially available products that can be suitably used as the glycidyl group-containing compound include UVR-6216 (manufactured by Union Carbide), glycidol, AOEX24, cyclomer A200, (manufactured by Daicel Chemical Industries, Ltd.), Epicoat 828, Epicoat 812, Epicoat 1031, Epicoat 872, Epicoat CT508 (above, manufactured by Yuka Shell Co., Ltd.), KRM-2400, KRM-2410, KRM-2408, KRM-2490, KRM-2720, KRM-2750 (above, Asahi Denka Kogyo ( Product)). These can be used alone or in combination of two or more.

  Moreover, the manufacturing method does not ask | require these epoxy compounds. For example, Maruzen KK publication, 4th edition experimental chemistry course 20 organic synthesis II, 213, 1992, Ed. By Alfred Hasfner, The Chemistry of Heterocyclic compounds, Vol. 30, Advertisement, Small Ring Heterocycle part3 Oxilane, John & Wiley and Sons, An Inc No. 5, 42, 1986, Yoshimura, Adhesion, Vol. 30, No. 7, 42, 1986, Japanese Patent Application Laid-Open No. 11-1000037, Japanese Patent No. 2906245, Japanese Patent No. 2926262, and the like.

  As an epoxy compound, you may use the commercially available epoxy composition by which 2 or more types of components were mixed and prepared previously according to use conditions. These are commercially available as adhesives or sealants. Commercial products can be obtained from, for example, Three Bond, EMI, Tesque and the like. Specifically, OPTOCAST (trade name) 3505, 3506, 3553, and Tesque A-1771 (trade name) manufactured by EMI are exemplified. However, the present invention is not limited to these.

  The quantum dot-containing polymerizable composition can contain a polymerization initiator. Specifically, a known radical polymerization initiator or cationic polymerization initiator can be included as the polymerization initiator. As for the polymerization initiator, for example, paragraphs 0037 of JP2013-043382A and paragraphs 0040-0042 of JP2011-159924A can be referred to. The polymerization initiator is preferably 0.1 mol% or more, more preferably 0.5 to 5 mol% of the total amount of the polymerizable compounds contained in the polymerizable composition. However, since the acid generator may act as a polymerization initiator for the polymerizable compound, the use of the polymerization initiator is not essential. As the polymerization initiator, a photopolymerization initiator or a thermal polymerization initiator may be appropriately selected according to the type of the polymerizable compound. The polymerization treatment is preferably performed by light irradiation in that the polymerization treatment is completed in a short time. Therefore, from this point, a photopolymerization initiator is preferable as the polymerization initiator.

  Some acid generators function as a cationic polymerization initiator capable of initiating polymerization of a cationically polymerizable compound. When such an acid generator is used, the polymerizable compound contained in the quantum dot-containing polymerizable composition is a cationic polymerizable compound capable of initiating a polymerization reaction by releasing a protonic acid from the acid generator. It is not essential to add a polymerization initiator separately and use it together. On the other hand, from the viewpoint of further improving the adhesion, the polymerizable compound is preferably a radical polymerizable compound. In view of this, preferred polymerizable compounds include the monofunctional (meth) acrylate compounds and polyfunctional (meth) acrylate compounds described above.

-Other components-
The quantum dot-containing composition can be prepared by using the above-described components and known additives that can be optionally added as necessary. For example, a quantum dot-containing composition can be prepared by simultaneously or sequentially mixing the above components and one or more known additives added as necessary. The amount of additive used is not particularly limited and can be set as appropriate. Moreover, you may add a solvent as needed for the viscosity etc. of a quantum dot containing composition. In this case, the type and amount of the solvent used are not particularly limited. For example, one or a mixture of two or more organic solvents can be used as the solvent.

The quantum dot-containing composition may contain an acid generator that generates a protonic acid by applying energy. In the case of an acid generator that generates a protonic acid by applying energy (trigger), for example, the protonic acid can be generated by applying energy after bringing the composition into contact with the adjacent layer surface. As a result of the acceleration of the reaction of the organometallic coupling agent by the protonic acid generated from the acid generator in this manner, the present inventors presume that the adhesion with the adjacent layer is improved.
From the above viewpoint, it is preferable that the quantum dot-containing composition does not contain a large amount of proton acid in a state that does not generate proton acid by applying energy. Specifically, the content of such a protonic acid is preferably 20 parts by mass or less, preferably 10 parts by mass or less, and preferably 5 parts by mass or less with respect to 100 parts by mass of the organometallic coupling agent. Is more preferable, and 0 part by mass is most preferable.
Moreover, in the manufacturing method of the wavelength conversion member of this invention, before laminating | stacking the inorganic layer of a barrier film, and the wavelength conversion layer containing a quantum dot, the surface of the inorganic layer of a barrier film contains an organometallic coupling agent and water beforehand. Because the surface treatment with the composition provides sufficiently good adhesion after wet heat aging between the wavelength conversion layer containing the quantum dots and the barrier film, the quantum dot-containing composition is a reaction such as an acid generator. An accelerator may not be included. Specifically, the content of the reaction accelerator such as an acid generator is preferably 20 parts by mass or less, preferably 10 parts by mass or less, with respect to 100 parts by mass of the organometallic coupling agent. The amount is more preferably equal to or less than part by mass, and most preferably 0 part by mass.

<Winding process>
It is preferable that the manufacturing method of the wavelength conversion member of this invention includes the process of winding up the above-mentioned wavelength conversion member on a roll after the above-mentioned lamination process.
Moreover, the wavelength conversion member manufacturing method of the present invention includes a quantum dot-containing wavelength by performing the above-described unwinding step, the above-described surface treatment step, the above-described laminating step, and the above-described winding step by a roll-to-roll. It is preferable from the viewpoint that a wavelength conversion member having good adhesion after wet heat aging between the conversion layer and the barrier film can be produced with high productivity.

[Wavelength conversion member]
The 1st aspect of the wavelength conversion member of this invention is the wavelength conversion member manufactured with the manufacturing method of the wavelength conversion member of this invention.
A second aspect of the wavelength conversion member of the present invention contains a barrier film having at least one inorganic layer subjected to surface treatment, and quantum dots arranged in direct contact with the surface-treated surface of the barrier film. The wavelength conversion member is a surface conversion composition that is applied to the surface of the inorganic layer of the barrier film with a surface treatment composition containing a solvent containing water and an organic metal coupling agent.
Hereinafter, the wavelength conversion member of the present invention will be described in more detail.

In the wavelength conversion member of the present invention, the concentration of the organometallic coupling agent in the surface region at a distance of 10% or less in the thickness direction from at least one surface of the wavelength conversion layer is 10 in the thickness direction from both surfaces of the wavelength conversion layer. Higher than the concentration of the organometallic coupling agent in the internal region at a distance exceeding% is preferable from the viewpoint of good adhesion after aging with heat and heat between the wavelength conversion layer containing the quantum dots and the barrier film.
The concentration of the organometallic coupling agent in the surface region at a distance of 10% or less in the thickness direction from at least one surface of the wavelength conversion layer is in the inner region at a distance exceeding 10% in the thickness direction from both surfaces of the wavelength conversion layer. That it is higher than the density | concentration of an organometallic coupling agent can be measured by the method as described in the below-mentioned Example.

[Backlight unit]
The backlight unit of the present invention includes at least the wavelength conversion member of the present invention and a light source. The details of the wavelength conversion member are as described above.

(Emission wavelength of backlight unit)
From the viewpoint of realizing high luminance and high color reproducibility, it is preferable to use a backlight unit that has been converted to a multi-wavelength light source. As a preferred embodiment,
Blue light having an emission center wavelength in a wavelength band of 430 to 480 nm and a peak of emission intensity having a half width of 100 nm or less;
Green light having an emission center wavelength in a wavelength band of 500 to 600 nm and a peak of emission intensity having a half width of 100 nm or less;
Red light having an emission center wavelength in a wavelength band of 600 to 680 nm and a peak of emission intensity having a half-value width of 100 nm or less;
And a backlight unit that emits light.
From the viewpoint of further improving luminance and color reproducibility, the wavelength band of the blue light emitted from the backlight unit is preferably in the range of 440 to 480 nm, and more preferably in the range of 440 to 460 nm.
From the same viewpoint, the wavelength band of the green light emitted from the backlight unit is preferably in the range of 510 to 560 nm, and more preferably in the range of 510 to 545 nm.
From the same viewpoint, the wavelength band of red light emitted from the backlight unit is preferably in the range of 600 to 650 nm, and more preferably in the range of 610 to 640 nm.

  From the same viewpoint, the half-value widths of the emission intensity of blue light, green light, and red light emitted from the backlight unit are all preferably 80 nm or less, more preferably 50 nm or less, and 40 nm or less. More preferably, it is more preferably 30 nm or less. Among these, it is particularly preferable that the half-value width of each emission intensity of blue light is 25 nm or less.

The backlight unit includes a light source together with at least the wavelength conversion member. In one embodiment, a light source that emits blue light having an emission center wavelength in a wavelength band of 430 nm to 480 nm, for example, a blue light emitting diode that emits blue light can be used. In the case of using a light source that emits blue light, the wavelength conversion layer preferably includes at least quantum dots A that are excited by excitation light and emit red light, and quantum dots B that emit green light. Thereby, white light can be embodied by blue light emitted from the light source and transmitted through the wavelength conversion member, and red light and green light emitted from the wavelength conversion member.
Alternatively, in another aspect, a light source that emits ultraviolet light having an emission center wavelength in a wavelength band of 300 nm to 430 nm, for example, an ultraviolet light emitting diode can be used. In this case, it is preferable that the wavelength conversion layer includes quantum dots C that are excited by excitation light and emit blue light together with quantum dots A and B. Thereby, white light can be embodied by red light, green light, and blue light emitted from the wavelength conversion member.
In another aspect, two types of light sources selected from the group consisting of a blue laser that emits blue light, a green laser that emits green light, and a red laser that emits red light are used. By having quantum dots emitting fluorescent light with different emission wavelengths in the wavelength conversion layer, white light is realized by the two types of light emitted from the light source and the light emitted from the quantum dots in the wavelength conversion layer. It can also be converted.
In other embodiments, the light emitting diode can be replaced with a laser light source.
In the backlight unit of the present invention, the aforementioned light source preferably has a light emission center wavelength in a wavelength band of 430 nm to 480 nm.

(Configuration of backlight unit)
The configuration of the backlight unit may be an edge light system using a light guide plate or a reflection plate as a constituent member, or a direct type. FIG. 1 shows an example of an edge light type backlight unit as one mode. Any known light guide plate can be used without any limitation.

  The backlight unit can also include a reflecting member at the rear of the light source. There is no restriction | limiting in particular as such a reflecting member, A well-known thing can be used, and it is described in patent 3416302, patent 3363565, patent 4091978, patent 3448626, etc., The content of these gazettes is this Incorporated into the invention.

  In addition, the backlight unit preferably includes a known diffusion plate, diffusion sheet, prism sheet (for example, BEF series manufactured by Sumitomo 3M Limited), and a light guide. Other members are also described in each publication such as Japanese Patent No. 3416302, Japanese Patent No. 3363565, Japanese Patent No. 4091978, Japanese Patent No. 3448626, and the contents of these publications are incorporated in the present invention.

[Liquid Crystal Display]
The liquid crystal display device of the present invention includes at least the backlight unit of the present invention and a liquid crystal cell.

(Configuration of liquid crystal display device)
The driving mode of the liquid crystal cell is not particularly limited, and twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), in-plane switching (IPS), optically compensated bend cell (OCB) Various modes such as can be used. The liquid crystal cell is preferably VA mode, OCB mode, IPS mode, or TN mode, but is not limited thereto. As an example of the configuration of the VA mode liquid crystal display device, the configuration shown in FIG. However, the specific configuration of the liquid crystal display device is not particularly limited, and a known configuration can be adopted.

  In one embodiment of the liquid crystal display device, a liquid crystal cell having a liquid crystal layer sandwiched between substrates provided with electrodes on at least one of the opposite sides is provided, and the liquid crystal cell is arranged between two polarizing plates. The liquid crystal display device includes a liquid crystal cell in which liquid crystal is sealed between upper and lower substrates, and displays an image by changing the alignment state of the liquid crystal by applying a voltage. Furthermore, it has an accompanying functional layer such as a polarizing plate protective film, an optical compensation member that performs optical compensation, and an adhesive layer as necessary. In addition to (or instead of) color filter substrates, thin layer transistor substrates, lens films, diffusion sheets, hard coat layers, antireflection layers, low reflection layers, antiglare layers, etc., forward scattering layers, primer layers, antistatic layers Further, a surface layer such as an undercoat layer may be disposed.

FIG. 2 illustrates an example of a liquid crystal display device according to one embodiment of the present invention. The liquid crystal display device 51 shown in FIG. 2 has the backlight side polarizing plate 14 on the surface of the liquid crystal cell 21 on the backlight side. The backlight-side polarizing plate 14 may or may not include the polarizing plate protective film 11 on the backlight-side surface of the backlight-side polarizer 12, but it is preferably included.
The backlight side polarizing plate 14 preferably has a configuration in which the polarizer 12 is sandwiched between two polarizing plate protective films 11 and 13.
In this specification, the polarizing plate protective film on the side closer to the liquid crystal cell with respect to the polarizer is referred to as the inner side polarizing plate protective film, and the polarizing plate protective film on the side farther from the liquid crystal cell with respect to the polarizer is referred to as the outer side polarizing plate. It is called a protective film. In the example shown in FIG. 2, the polarizing plate protective film 13 is an inner side polarizing plate protective film, and the polarizing plate protective film 11 is an outer side polarizing plate protective film.

  The backlight side polarizing plate may have a retardation film as an inner side polarizing plate protective film on the liquid crystal cell side. As such a retardation film, a known cellulose acylate film or the like can be used.

  The liquid crystal display device 51 includes a display side polarizing plate 44 on the surface of the liquid crystal cell 21 opposite to the surface on the backlight side. The display-side polarizing plate 44 has a configuration in which a polarizer 42 is sandwiched between two polarizing plate protective films 41 and 43. The polarizing plate protective film 43 is an inner side polarizing plate protective film, and the polarizing plate protective film 41 is an outer side polarizing plate protective film.

  The backlight unit 1 included in the liquid crystal display device 51 is as described above.

  There is no particular limitation on the liquid crystal cell, the polarizing plate, the polarizing plate protective film, and the like constituting the liquid crystal display device according to one embodiment of the present invention, and those prepared by known methods and commercially available products can be used without any limitation. it can. It is of course possible to provide a known intermediate layer such as an adhesive layer between the layers.

  Hereinafter, the present invention will be described more specifically based on examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

[Example 1]
1. Preparation of barrier film 10 An organic layer and an inorganic layer are formed on one side of a polyethylene terephthalate film (PET film, manufactured by Toyobo Co., Ltd., trade name: Cosmo Shine (registered trademark) A4300, thickness 50 μm, width 1000 mm, length 100 m) by the following procedure Layers were formed sequentially.
Prepare trimethylolpropane triacrylate (TMCTA manufactured by Daicel Cytec Co., Ltd.) and a photopolymerization initiator (manufactured by Lamberti Co., ESACURE KTO46), and weigh them so that the former: latter = 95: 5. It was dissolved in methyl ethyl ketone to obtain a coating solution having a solid concentration of 15%. This coating solution was applied onto the PET film by a roll-to-roll using a die coater, and passed through a 50 ° C. drying zone for 3 minutes. Thereafter, the sample was irradiated with ultraviolet rays (integrated irradiation amount: about 600 mJ / cm ² ) in a nitrogen atmosphere, cured by ultraviolet curing, and wound up. The thickness of the first organic layer formed on the support was 1 μm.

Next, an inorganic layer (silicon nitride layer) was formed on the surface of the first organic layer using a roll-to-roll CVD (Chemical Vapor Deposition) apparatus. Silane gas (flow rate 160 sccm), ammonia gas (flow rate 370 sccm), hydrogen gas (flow rate 590 sccm), and nitrogen gas (flow rate 240 sccm) were used as source gases. A high frequency power supply having a frequency of 13.56 MHz was used as the power supply. The film formation pressure was 40 Pa, and the ultimate film thickness was 50 nm. In this way, two barrier films 10 having an inorganic layer laminated on the surface of the first organic layer were produced.
The contact angle with water on the surface of the inorganic layer of the obtained barrier film 10 was 50 degrees. It was confirmed that the oxygen permeability of the barrier film 10 was 0.01 cm ³ / (m ² · day · atm) or less, and the total light transmittance in the visible light region was 90% or more.

2. Surface treatment with organometallic coupling agent A solution having the following composition was prepared and used as a surface treatment composition (surface treatment coating solution).
IPA / ethanol / acetic acid / water / KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) = 14/14/2/20/50 mass%, pH = 4.5.
IPA is an abbreviation for isopropanol, and KBM-5103 is a solution containing a silane coupling agent, which is one of organometallic coupling agents.
This surface treatment composition (surface treatment coating solution) is applied on the inorganic layer of the barrier film by a roll-to-roll using a die coater at a coating amount of ² cc / m ² and dried at 120 ° C. For 3 minutes.

3. Lamination (wavelength conversion layer production)
The following quantum dot dispersion liquid 1 was prepared as a quantum dot-containing polymerizable composition, filtered through a polypropylene filter having a pore size of 0.2 μm, dried under reduced pressure for 30 minutes, and used as a coating liquid. The quantum dot concentration in the following toluene dispersion was 1% by mass.

──────────────────────────────────────
Quantum dot dispersion 1
──────────────────────────────────────
Toluene dispersion of quantum dots 1 (light emission maximum: 520 nm) 10 parts by weight Toluene dispersion of quantum dots 2 (issue maximum: 630 nm) 1 part by weight lauryl methacrylate 80.8 parts by weight trimethylolpropane triacrylate 18.2 parts by weight light 1 part by mass of a polymerization initiator (Irgacure (registered trademark) 819 (manufactured by BASF Corporation)
──────────────────────────────────────

As the quantum dots 1 and 2, nanocrystals having the following core-shell structure (InP / ZnS) were used.
Quantum dot 1: INP530-10 (manufactured by NN-labs)
Quantum dot 2: INP620-10 (manufactured by NN-labs)
The viscosity of the quantum dot dispersion liquid 1 was 50 mPa · s.

Silane coupling agent KBM-5103

Using the barrier film 10 produced by the above-described procedure as the first and second films, the wavelength conversion member 1 was obtained by the manufacturing process described with reference to FIGS. 3 and 4. Specifically, while the first barrier film 10 is continuously conveyed at a tension of 1 m / min and 60 N / m as the first film, the coating liquid that is a quantum dot-containing composition is applied from the die coater to the first film. Was applied to the surface of the film to form a coating film having a thickness of 50 μm. Next, the first film on which the coating film was formed was wound around a backup roller, and a second film, which was another second barrier film 10, was laminated on the coating film. The film was wound around a backup roller with the coating film sandwiched between the first film and the second film, and irradiated with ultraviolet rays while being continuously conveyed. The diameter of the backup roller was φ300 mm, and the temperature of the backup roller was 50 ° C. The irradiation amount of ultraviolet rays was 2000 mJ / cm ² . L1 was 50 mm, L2 was 1 mm, and L3 was 50 mm.
The coating film was cured by irradiation of ultraviolet rays to form a wavelength conversion layer (cured layer), and the wavelength conversion member 1 that was a laminate obtained on another collection roll was wound up and manufactured. The thickness of the cured layer of the wavelength conversion member was about 50 μm. Thus, the wavelength conversion member of Example 1 which has the barrier films 10 on both surfaces of the wavelength conversion layer, respectively, and both main surfaces of the wavelength conversion layer are in direct contact with the inorganic layer formed by the surface treatment of the barrier film 10. 1 was obtained.

[Example 2]
In Example 1, the wavelength conversion member 2 of Example 2 was produced in the same manner as in Example 1 except that the composition for surface treatment (surface treatment coating solution) was changed to the following composition.
IPA / ethanol / acetic acid / water / KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) / F-444 (manufactured by DIC) = 14/14/2/20/50 / 0.1 mass%, pH = 4. 6.
In Table 2 below, F-444, which is a fluorine-based nonionic surfactant manufactured by DIC, is described as surfactant A.

[Example 3]
In Example 1, the wavelength conversion member 3 of Example 3 was produced in the same manner as in Example 1 except that the surface treatment composition (surface treatment coating solution) was changed to the following composition.
IPA / ethanol / acetic acid / water / KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) / F-114 (manufactured by DIC) = 14/14/2/20/50 / 0.1 mass%, pH = 4. 4.
In Table 2 below, F-114, which is a fluorine-based anionic surfactant manufactured by DIC, is described as surfactant B.

[Example 4]
In Example 1, the wavelength conversion member 4 of Example 4 was produced in the same manner as in Example 1 except that the composition for surface treatment (surface treatment coating solution) was changed to the following composition.
IPA / ethanol / acetic acid / water / KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) / Neopelex G-15 (manufactured by Kao Corporation) = 14/14/2/20/50 / 0.6 mass%, pH = 4.5.
Neoperex G-15 (manufactured by Kao Corporation), a sodium dodecylbenzenesulfonate surfactant, and a solid content concentration of 16% are listed as surfactant C in Table 2 below.

[Example 5]
In Example 1, the wavelength conversion member 5 of Example 5 was produced in the same manner as in Example 1 except that the composition for surface treatment (surface treatment coating solution) was changed to the following composition.
IPA / ethanol / acetic acid / water / KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) / Emulgen 106 (manufactured by Kao Corporation) = 14/14/2/20/50 / 0.1 mass%, pH = 4. 7.
Emulgen 106 (manufactured by Kao Corporation), which is a polyoxyethylene lauryl ether surfactant, is listed as surfactant D in Table 2 below.

[Example 6]
In Example 1, the wavelength conversion member 6 of Example 6 was produced in the same manner as in Example 1 except that the composition for surface treatment (surface treatment coating solution) was changed to the following composition.
IPA / ethanol / acetic acid / water / KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) / Coatamine 24P (manufactured by Kao Corporation) = 14/14/2/20/50 / 0.1 mass%, pH = 4. 4.
Coatamine 24P (manufactured by Kao Corporation), which is a lauryltrimethylbenzylammonium chloride surfactant, is listed as surfactant E in Table 2 below.

[Example 7]
Example 1 except that KBM-5103 in the surface treatment composition (surface treatment coating solution) in Example 1 was changed to KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd.), which is a silane coupling agent. In the same manner as described above, the wavelength conversion member 7 of Example 7 was produced.

[Example 8]
In Example 1, the wavelength conversion member 8 was produced like Example 1 except having changed the inorganic layer of the barrier film into the following.
The film on which the organic layer was formed was set in a hollow cathode type ion plating apparatus. Then, silicon oxide (manufactured by High Purity Chemical Research Laboratories), which is an evaporation source material, was put into a hollow cathode ion plating apparatus and evacuated. After the degree of vacuum reached 5 × 10 ⁻⁴ Pa, 15 sccm of argon gas was introduced into the plasma gun, and plasma with a current of 110 A and a voltage of 90 V was generated. Plasma was bent in a predetermined direction by maintaining the inside of the chamber at 1 × 10 ⁻¹ Pa and magnetic force, and the evaporation source material was irradiated. The evaporation source material sublimated through a molten state. This ion plating was carried out for 10 seconds and deposited on the film to form an inorganic layer made of silicon oxide having a thickness of 50 nm. The contact angle with water of the inorganic layer of the obtained barrier film was 25 degrees. The oxygen permeability of the barrier film was 0.01 cm ³ / (m ² · day · atm) or less, and it was confirmed that the total light transmittance in the visible light region was 90% or more.

[Comparative Example 1]
In Example 1, the wavelength conversion member T of Comparative Example 1 was produced in the same manner as in Example 1 except that the composition for surface treatment was not applied.

[Comparative Example 2]
In Example 1, except that the surface treatment composition of Example 1 was changed to a surface treatment composition containing no IPA / ethanol / KBM-5103 = 25/25/50 mass% water. In the same manner as in Example 1, a wavelength conversion member of Comparative Example 2 was produced. In addition, KBM-5103 which is a solution containing a silane coupling agent does not contain water.

[Reference Example 1]
In Example 1, the surface treatment was not performed after the barrier film 10 was produced, and the following quantum dot dispersion 2 was used as the quantum dot-containing polymerizable composition, in the same manner as in Example 1, and in Reference Example 1. A wavelength conversion member was prepared. Details of the quantum dot dispersion 2 are shown below.
The following quantum dot dispersion liquid 2 was prepared as a quantum dot-containing polymerizable composition, filtered through a polypropylene filter having a pore diameter of 0.2 μm, dried under reduced pressure for 30 minutes, and used as a coating liquid. The quantum dot concentration in the following toluene dispersion was 1% by mass.

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Quantum dot dispersion 2
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Toluene dispersion of quantum dots 1 (light emission maximum: 520 nm) 10 parts by weight Toluene dispersion of quantum dots 2 (issue maximum: 630 nm) 1 part by weight lauryl methacrylate 80.8 parts by weight trimethylolpropane triacrylate 18.2 parts by weight light 1 part by mass of a polymerization initiator (Irgacure (registered trademark) 819 (manufactured by BASF Corporation)
Silane coupling agent 3 parts by mass (KBM-5103, Shin-Etsu Chemical Co., Ltd.)
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As the quantum dots 1 and 2, nanocrystals having the following core-shell structure (InP / ZnS) were used.
Quantum dot 1: INP530-10 (manufactured by NN-labs)
Quantum dot 2: INP620-10 (manufactured by NN-labs)
The viscosity of the quantum dot dispersion liquid 2 was 50 mPa · s.

[Evaluation]
<Surface wettability evaluation method>
If the composition for surface treatment can be applied to the entire surface of the inorganic layer when the composition for surface treatment is applied and dried on the surface of the inorganic layer of the barrier film: A
Some repelling occurs: B
Cannot be applied to the entire surface: C
It was determined.
The results are shown in Table 2 below.
If the evaluation is A or B, there is no practical problem. A rating is preferred.

<Evaluation of adhesion>
A sample was prepared by storing the prepared wavelength conversion member for 5 days under a high temperature and high humidity condition of 70 ° C. and 75%, and this sample was evaluated by a method in accordance with JIS K5400. Cuts that reach the wavelength conversion layer at 90 ° with respect to the film surface are made at 1 mm intervals on one side of the layer (barrier film) other than the wavelength conversion layer of the wavelength conversion member of each example, comparative example, and reference example. 100 squares of grids with an interval of 1 mm were produced. On top of this, the tape affixed with a 2 cm wide Mylar tape (manufactured by Nitto Denko, polyester tape, No. 31B) was peeled off. The evaluation was made based on the number of cells in which the outermost layer of the wavelength conversion member of each Example, Comparative Example, and Reference Example remained. The same test was performed on both sides, and evaluation was performed according to the following evaluation criteria using the value of the side with the smaller number of cells where the outermost layer remained. The results are shown in Table 2 below.
(Evaluation criteria)
A: Number of remaining cells 100 B: Number of remaining cells 99-80 C: Number of remaining cells 79-60 D: Number of remaining cells 59-20 E: Number of remaining cells 19-0 If A, B or C evaluation There is no practical problem. A or B evaluation is preferable, and A evaluation is more preferable.

From the said Table 2, it turned out that the wavelength conversion member of each Example has the favorable adhesiveness after the wet heat aging between the wavelength conversion layer containing a quantum dot, and a barrier film.
From the comparative example 1, it turned out that the wavelength conversion member manufactured using the barrier film which is not surface-treated has bad adhesiveness after the wet heat aging between the wavelength conversion layer containing a quantum dot, and a barrier film. .
From the comparative example 2, the wavelength conversion member manufactured using the composition for surface treatment which does not contain water may have poor adhesion after wet heat aging between the wavelength conversion layer containing the quantum dots and the barrier film. all right.

<Evaluation of uneven distribution of organometallic coupling agent>
Furthermore, the uneven distribution of the organometallic coupling agent in the wavelength conversion layer was evaluated for the wavelength conversion members of Examples, Comparative Examples, and Reference Examples.
Specifically, the concentration of the organometallic coupling agent in the surface region at a distance of 10% or less in the thickness direction from at least one surface of the wavelength conversion layer in the wavelength conversion member of each example is the surface of both wavelength conversion layers. It was confirmed by the following method that the concentration was higher than the concentration of the organometallic coupling agent in the internal region at a distance exceeding 10% in the thickness direction.
The film which is the produced wavelength conversion member was cut and the cross section was analyzed by X-ray photoelectron spectroscopy (XPS) to confirm the presence distribution of the coupling agent.
On the other hand, in the wavelength conversion members of Comparative Example 1 and Reference Example, the uneven distribution of the organometallic coupling agent in the wavelength conversion layer could not be measured by the above method.

[Examples 101 to 108, Comparative Examples 101 and 102, and Reference Example 101]
<Manufacture of backlight unit and liquid crystal display device>
A commercially available tablet terminal (Kindle (registered trademark) Fire HDX 7 ″ manufactured by Amazon) was disassembled and the backlight unit was taken out. Each of the examples cut out in a rectangular shape on the light guide plate of the taken out backlight unit, comparative examples and The wavelength conversion member of the reference example is placed, and two prism sheets whose surface uneven pattern directions are orthogonal are placed thereon, and the backlight units and liquid crystals of Examples 101 to 108, Comparative Examples 101 and 102, and Reference Example 101 are placed. A display device was produced.
It turned out that the wavelength conversion member of each Example has less peeling of the edge part at the time of cutting out into a rectangle compared with the wavelength conversion member of a comparative example.
Moreover, the liquid crystal display device of each Example showed the favorable display performance.

DESCRIPTION OF SYMBOLS 1 Backlight unit 1A Light source 1B Light guide plate 1C Wavelength conversion member 2 Blue light 3 Green light 4 Red light 10 1st film 11 Polarizing plate protective film 12 Polarizer 13 Polarizing plate protective film 14 Backlight side polarizing plate 20 Application | coating part 21 Liquid crystal cell 22 Coating film 24 Die coater 26 Backup roller 28 Wavelength conversion layer (cured layer)
30 Laminating unit 32 Laminating roller 34 Heating chamber 41 Polarizing plate protective film 42 Polarizer 43 Polarizing plate protective film 44 Display side polarizing plate 50 Second film 51 Liquid crystal display device 60 Curing unit 62 Backup roller 64 Ultraviolet irradiation device 70 Wavelength converting member 80 Peeling roller 100 Manufacturing equipment

  The present invention is useful in the field of manufacturing liquid crystal display devices.

Claims (13)

A surface treatment step of surface-treating a barrier film having at least one inorganic layer;
A lamination step of laminating a wavelength conversion layer containing quantum dots on the surface-treated surface of the barrier film,
The method for producing a wavelength conversion member, wherein the surface treatment step is a step of applying a surface treatment composition containing a solvent containing water and an organic metal coupling agent to the surface of the inorganic layer of the barrier film.   The manufacturing method of the wavelength conversion member of Claim 1 with which the said organometallic coupling agent has a reactive functional group at the terminal.   The manufacturing method of the wavelength conversion member of Claim 1 or 2 with which the said composition for surface treatment contains surfactant.   The manufacturing method of the wavelength conversion member of Claim 3 whose said surfactant is a fluorine-type nonionic surfactant.   The manufacturing method of the wavelength conversion member as described in any one of Claims 1-4 which contains an organic solvent in the solvent of the said composition for surface treatment. The surface treatment step is a step of subjecting a first barrier film having at least one inorganic layer and a second barrier film having at least one inorganic layer, respectively, to surface treatment;
The wavelength conversion according to any one of claims 1 to 5, wherein the laminating step is a step of sandwiching the wavelength conversion layer between the surface-treated surfaces of the first barrier film and the second barrier film. Manufacturing method of member. Unwinding the first barrier film and the second barrier film from the rolls before the surface treatment step,
Including a step of winding the wavelength conversion member around a roll after the laminating step;
The method for producing a wavelength conversion member according to claim 6, wherein the unwinding step, the surface treatment step, the laminating step, and the winding step are performed by roll-to-roll.   The manufacturing method of the wavelength conversion member as described in any one of Claims 1-7 whose said lamination process is a coating process of a quantum dot containing composition. A barrier film having a surface-treated at least one inorganic layer;
A wavelength conversion layer containing quantum dots, disposed in direct contact with the surface-treated surface of the barrier film,
The wavelength conversion member which is the provision to the surface of the said inorganic layer of the said barrier film of the composition for surface treatments in which the said surface treatment contains the solvent and organic metal coupling agent containing water. The inside of the distance where the concentration of the organometallic coupling agent in the surface region at a distance of 10% or less in the thickness direction from at least one surface of the wavelength conversion layer exceeds 10% in the thickness direction from both surfaces of the wavelength conversion layer The wavelength conversion member according to claim 9, wherein the wavelength conversion member is higher than the concentration of the organometallic coupling agent in the region. The wavelength conversion member according to claim 9 or 10 ,
A light source;
Including at least a backlight unit. The backlight unit according to claim 11 , wherein the light source has an emission center wavelength in a wavelength band of 430 nm to 480 nm. The backlight unit according to claim 11 or 12 ,
A liquid crystal cell;
A liquid crystal display device comprising at least