WO2016039080A1

WO2016039080A1 - Functional laminate film and method for producing functional laminate film

Info

Publication number: WO2016039080A1
Application number: PCT/JP2015/073048
Authority: WO
Inventors: 英二郎岩瀬; 内海　京久
Original assignee: 富士フイルム株式会社
Priority date: 2014-09-12
Filing date: 2015-08-17
Publication date: 2016-03-17
Also published as: JPWO2016039080A1; JP6316443B2

Abstract

Provided are: a functional laminate film that can prevent the deterioration of a functional layer by minimizing the entrance of moisture and oxygen from an end surface of the functional layer and that makes it possible to increase the proportion of an area that can be effectively used as a functional layer without decreasing gas barrier properties; and a method for producing the functional laminate film. The functional laminate film comprises a functional layer and a two gas barrier films that comprise an inorganic layer and that are layered on each of the one main surface and the other main surface of the functional layer. The inorganic layer comprises silicon nitride. The functional layer comprises a compressed area on the ends thereof, said compressed area being thinner than the average thickness of the functional layer. The compressed area is an area within a range of 10 mm or less from the end surfaces of the functional layer and is thinnest at the end surfaces.

Description

Functional laminated film and method for producing functional laminated film

The present invention relates to a functional laminate film and a method of producing a functional laminate film.

Liquid crystal display devices (hereinafter also referred to as LCDs) consume less power, and their use is expanding year by year as a space-saving image display device. Further, in liquid crystal display devices in recent years, further power saving, color reproducibility improvement and the like are required as LCD performance improvement.

With the power saving of the backlight of the LCD, it has been proposed to use a quantum dot that converts the wavelength of incident light and emits it in order to improve light utilization efficiency and improve color reproducibility. .
A quantum dot is a state of electrons whose movement direction is restricted in all three dimensions, and when semiconductor nanoparticles are three-dimensionally surrounded by a high potential barrier, these nanoparticles It becomes a dot. Quantum dots exhibit various quantum effects. For example, the “quantum size effect” occurs in which the density of states (energy levels) of electrons is discretized. According to this quantum size effect, it is possible to control the light absorption wavelength and the light emission wavelength by changing the size of the quantum dot.

In general, such quantum dots are dispersed in a resin or the like and, for example, are disposed and used as a quantum dot film for wavelength conversion between a backlight and a liquid crystal panel.
When excitation light enters the film containing quantum dots from the backlight, the quantum dots are excited to emit fluorescence. Here, by using quantum dots having different light emission characteristics, white light can be embodied by emitting light with a narrow half-width of red light, green light, and blue light. Since the half width of the fluorescence due to the quantum dot is narrow, it is possible to make the white light obtained by selecting the wavelength highly bright or to be designed to be excellent in color reproducibility.

By the way, quantum dots are easily degraded by moisture and oxygen, and there is a problem that the light emission intensity is reduced by the photooxidation reaction. Therefore, a gas barrier film is laminated | stacked on both surfaces of the resin layer (henceforth a "quantum dot layer") containing a quantum dot, and protecting a quantum dot layer is performed.
However, only protecting both main surfaces of the quantum dot layer with the gas barrier film causes a problem that moisture and oxygen infiltrate from the end face not protected by the gas barrier film and the quantum dots are degraded.
On the other hand, it is conceivable to mix a material that is difficult to pass moisture or oxygen into the functional layer, but there is a problem that the selection range of the material becomes narrow or the productivity decreases.
Therefore, it has been proposed to seal the end face with a gas barrier film to reduce the infiltration of moisture and oxygen from the end of the quantum dot layer to prevent the deterioration of the quantum dot.

For example, Patent Document 1 describes a display backlight unit comprising a remote phosphor film comprising a light emitting quantum dot (QD) population, sandwiching the QD phosphor material with two gas barrier films, and two gas barrier films A configuration for narrowing and sealing the end is described. Moreover, oxides, such as a silicon oxide, a titanium oxide, and aluminum oxide, are described as a formation material of the barrier layer of a gas barrier film.

Japanese Patent Publication No. 2012-544018

By the way, in recent years, in the LCD, there is a demand for further thinning. Therefore, the quantum dot layer is required to be able to express a desired wavelength conversion function and to be formed as thin as possible.
Furthermore, in the LCD, it is required to further increase the ratio of the display area (light emitting area) to the entire display device, and further narrowing of the frame portion is required.

Therefore, if the gas barrier film is narrowed to seal the end in order to reduce the infiltration of moisture and oxygen from the end of the quantum dot layer, the thickness of the quantum dot layer at the end becomes thinner. At the end of the quantum dot layer, its function can not be sufficiently expressed, and the size of the area that can be effectively used may be reduced, and the frame portion may be enlarged.
On the other hand, it is conceivable to reduce the frame portion and increase the area that can be effectively used by forming the thickness so as to be suddenly reduced near the end face. However, since a barrier layer made of an oxide such as silicon oxide, titanium oxide, or aluminum oxide is hard and brittle, the barrier layer may have a barrier layer using such an oxide as a forming material. As a result, there is a problem that the gas barrier property is lowered and it is impossible to suppress the infiltration of water and oxygen into the quantum dot layer.

The object of the present invention is to solve the problems of the prior art as described above, and it is possible to suppress the infiltration of water and oxygen from the end face of the functional layer to prevent the deterioration of the functional layer, and to have gas barrier properties. It is an object of the present invention to provide a functional laminated film and a method for producing a functional laminated film which can increase the proportion of the area which can be effectively used as a functional layer without lowering the

As a result of earnest studies to achieve the above problems, the inventor of the present invention has a functional layer, and two gas barrier films having an inorganic layer, which are respectively laminated on one main surface and the other main surface of the functional layer. In the functional laminated film, the inorganic layer contains silicon nitride, and the functional layer has at the end a throttling area thinner than the average thickness of the functional layer, and the throttling area is 10 mm from the end face of the functional layer In the region of the following range, and the thickness at the end face being the thinnest, it is possible to suppress the infiltration of moisture or oxygen from the end face of the functional layer, and prevent the deterioration of the functional layer, and the gas barrier property In the present invention, the inventors have found that it is possible to increase the proportion of the area that can be effectively used as a functional layer without lowering the
That is, the present invention provides a functional laminated film having the following constitution and a method for producing the same.

(1) A functional laminate film having a functional layer and two gas barrier films having an inorganic layer, which are respectively laminated on one principal surface and the other principal surface of the functional layer,
The inorganic layer comprises silicon nitride and
The functional layer has at the end a throttling area that is thinner than the average thickness of the functional layer,
The squeeze area is an area within 10 mm or less from the end face of the functional layer, and the functional laminated film having the thinnest thickness at the end face.
(2) The functional laminated film according to (1), wherein the squeeze area is an area in the range of 1 mm or less from the end face.
(3) The functional laminated film according to (1) or (2), wherein the thickness at the end face of the functional layer is 50% or less of the average thickness of the functional layer.
(4) The functional laminated film according to any one of (1) to (3), wherein the ends of the two gas barrier films are in contact with each other.
(5) The functional laminated film according to any one of (1) to (4), wherein the thickness of the functional layer on the inner side of the narrowed region is ± 2% of the average thickness of the functional layer.
(6) The functional laminated film according to any one of (1) to (5), wherein the uppermost layer on the functional layer side of the gas barrier film is an inorganic layer.
(7) The gas barrier film according to any one of (1) to (6), having a gas barrier support, an organic layer laminated on the gas barrier support, and an inorganic layer laminated on the organic layer Laminated film.
(8) The functional laminated film according to any one of (1) to (7), wherein the thickness of the gas barrier film is 5 μm to 100 μm.
(9) The functional laminated film according to (7) or (8), wherein the gas barrier support has a melting point of 230 ° C. or less and a glass transition temperature of 120 ° C. or less.
(10) Any one of (1) to (9) in which the water vapor transmission rate after extending the gas barrier film in the plane direction by 2.5% is 1 × 10 ⁻³ [g / (m ² · day)] or less Functional laminated film as described in.
(11) The functional laminated film according to any one of (1) to (10), wherein the inorganic layer has a hydrogen content of 10 atomic% to 30 atomic%.
(12) The functional laminated film according to any one of (1) to (11), wherein the functional layer is a quantum dot layer containing a large number of quantum dots.
(13) A preparing step of preparing a laminate having a functional layer, and two gas barrier films having an inorganic layer containing silicon nitride, which are respectively laminated on one main surface and the other main surface of the functional layer;
Cutting the laminate to form a thickness of the functional layer in a range of 10 mm or less from the cut surface, thinner than the average thickness of the functional layer, and the thinnest on the cut surface. Method for producing functional laminated film.
(14) The gas barrier film has a gas barrier support and an inorganic layer,
The method for producing a functional laminated film according to (13), wherein the cutting is performed by heating the blade temperature to the range of the glass transition temperature + 50 ° C to the melting point + 50 ° C of the gas barrier support.
(15) The manufacturing method of the functional laminated film as described in (13) or (14) which performs a cutting process using a Thomson blade, a cutting blade, or a slitter blade.

According to the present invention as described above, it is possible to suppress the infiltration of moisture or oxygen from the end face of the functional layer, to prevent the deterioration of the functional layer, and to effectively use it as the functional layer without lowering the gas barrier properties. It is possible to provide a functional laminated film and a method for producing a functional laminated film that can increase the proportion of the possible regions.

FIG. 1 is a cross-sectional view conceptually showing one example of the functional laminate film of the present invention. It is sectional drawing which shows notionally an example of the gas barrier film used for a functional laminated film. It is sectional drawing which expands and shows the edge part of the functional laminated film shown in FIG. It is an expanded sectional view which shows notionally another example of the functional laminated film of this invention. FIGS. 5 (A) to 5 (C) are cross-sectional views conceptually showing one example of a functional laminate film, for explaining the manufacturing method of the present invention.

Hereinafter, the functional laminated film of the present invention and the method for producing the functional laminated film will be described in detail based on the preferred embodiments shown in the attached drawings.
Although the description of the configuration requirements described below may be made based on the representative embodiments of the present invention, the present invention is not limited to such embodiments.
In the present specification, a numerical range represented using “to” means a range including numerical values described before and after “to” as the lower limit value and the upper limit value.

FIG. 1 is a cross-sectional view conceptually showing one example of the functional laminate film of the present invention.

The functional laminated film 10 shown in FIG. 1 has two gas barrier films 14 laminated respectively on both main surfaces of the functional layer 12 and the functional layer 12, and the gap between the gas barrier films 14 is narrowed at the end. The thickness of the functional layer 12 is smaller than that of the central portion.

The functional layer 12 is a layer for expressing a desired function such as wavelength conversion.
As shown in FIG. 1, the functional layer 12 has a substantially uniform thickness in the central portion, and has an area in which the thickness gradually decreases at the end, and has a shape in which the thickness at the end is the smallest. The gradually thinning area at this end is the throttling area in the present invention.
This point will be described in detail later.

As an example, the functional layer 12 is a quantum dot layer formed by dispersing a large number of quantum dots in a matrix such as a resin, and has a function of converting the wavelength of light incident on the functional layer 12 and emitting it. .
For example, when blue light emitted from a backlight (not shown) is incident on the functional layer 12, the functional layer 12 has a wavelength of at least a part of the blue light as red light or green light due to the effect of quantum dots contained therein. Convert and emit.

Here, blue light is light having an emission center wavelength in a wavelength band of 400 nm to 500 nm, green light is light having an emission center wavelength in a wavelength band of 500 nm to 600 nm, and red light Is light having an emission center wavelength in a wavelength band of more than 600 nm and not more than 680 nm.
The wavelength conversion function expressed by the quantum dot layer is not limited to the configuration for wavelength converting blue light to red light or green light, and it is possible to convert at least a part of incident light to light of different wavelengths. Just do it.

The quantum dot is excited at least by the incident excitation light to emit fluorescence.
The type of quantum dot contained in the quantum dot layer is not particularly limited, and various known quantum dots may be appropriately selected according to the required wavelength conversion performance and the like.

With regard to quantum dots, reference can be made to, for example, JP-A-2012-169271 paragraphs 0060 to 0066, but the present invention is not limited to those described herein. As a quantum dot, a commercial item can be used without any restriction. The emission wavelength of the quantum dot can usually be adjusted by the composition and size of the particle.

The quantum dots are preferably distributed uniformly in the matrix, but may be distributed in the matrix with bias.
Further, only one type of quantum dot may be used, or two or more types may be used in combination.
When two or more types are used in combination, two or more types of quantum dots having different wavelengths of emitted light may be used.

Specifically, known quantum dots include a quantum dot (A) having an emission center wavelength in a wavelength range of 600 nm to 680 nm, a quantum dot (B) having an emission center wavelength in a wavelength range of 500 nm to 600 nm ), A quantum dot (C) having an emission center wavelength in a wavelength band of 400 nm to 500 nm, the quantum dot (A) is excited by excitation light to emit red light, and the quantum dot (B) is green light The quantum dot (C) emits blue light. For example, when blue light is made incident as excitation light to a quantum dot-containing laminate including quantum dots (A) and quantum dots (B), red light emitted by quantum dots (A) and light emitted by quantum dots (B) White light can be embodied by the green light being emitted and the blue light transmitted through the quantum dot layer. Alternatively, red light emitted by the quantum dot (A), quantum dot (B), by causing ultraviolet light as excitation light to enter the quantum dot layer containing the quantum dots (A), (B), and (C) White light can be embodied by the green light emitted by the light emitting diode and the blue light emitted by the quantum dot (C).

Further, as a quantum dot, a so-called quantum rod having a rod-like shape and having directivity and emitting polarized light may be used.

There is no particular limitation on the type of matrix of the quantum dot layer, and various resins used in known quantum dot layers can be used.
For example, polyester resins (for example, polyethylene terephthalate, polyethylene naphthalate), (meth) acrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins and the like can be mentioned. Alternatively, a curable compound having a polymerizable group can be used as a matrix. The type of the polymerizable group is not particularly limited, but is preferably a (meth) acrylate group, a vinyl group or an epoxy group, more preferably a (meth) acrylate group, and still more preferably an acrylate group. Moreover, as for the polymerizable monomers having two or more polymerizable groups, the respective polymerizable groups may be the same or different.

Specifically, for example, a resin containing the following first polymerizable compound and second polymerizable compound can be used as a matrix.

The first polymerizable compound is one or more selected from the group consisting of a bifunctional or higher functional (meth) acrylate monomer, and a monomer having two or more functional groups selected from the group consisting of an epoxy group and an oxetanyl group. Preferably it is a compound.

Among the bifunctional or higher (meth) acrylate monomers, examples of the difunctional (meth) acrylate monomer include neopentyl glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate ) Acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate hydroxypivalate, polyethylene glycol di (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclo Pentenyloxyethyl (meth) acrylate, dicyclopentanyl di (meth) acrylate and the like are mentioned as preferable examples.

Further, among the bifunctional or higher functional (meth) acrylate monomers, as the trifunctional or higher functional (meth) acrylate monomers, ECH modified glycerol tri (meth) acrylate, EO modified glycerol tri (meth) acrylate, PO modified glycerol tri (meth) ) Acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, EO modified phosphate triacrylate, trimethylolpropane tri (meth) acrylate, caprolactone modified trimethylolpropane tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate PO-modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, dipentaerythritol hexa (meth) a Lilate, dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, dipentaerythritol hydroxypenta (meth) acrylate, alkyl modified dipentaerythritol penta (meth) acrylate, dipentaerythritol poly (meth) Acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol ethoxy tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate and the like are mentioned as preferable examples.

Examples of the monomer having two or more functional groups selected from the group consisting of an epoxy group and an oxetanyl group include aliphatic cyclic epoxy compounds, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, bromine Brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, 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 ether; poly (polyether polyols) obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin Glycidyl ethers; diglycidyl esters of aliphatic long-chain dibasic acids; glycidyl esters of higher fatty acids; compounds containing epoxy cycloalkane and the like are suitably used.

Commercially available products that can be suitably used as a monomer having two or more functional groups selected from the group consisting of an epoxy group and an oxetanyl group include: Celoxide 2021 P, Celoxide 8000, manufactured by Sigma Aldrich, 4-cell manufactured by Daicel Chemical Industries, Ltd. Vinylcyclohexene dioxide and the like can be mentioned. These can be used singly or in combination of two or more.

The monomer having two or more functional groups selected from the group consisting of an epoxy group and an oxetanyl group may be produced by any method, for example, Maruzen KK Publishing, Fourth Edition Experimental Chemistry Lecture 20 Organic Synthesis II, 213 ~, 1992 Ed. By Alfred Hasfner, The chemistry of heterocyclic compounds-Small Ring Heterocycles part 3 Oxiranes, John & Wiley and Sons, An Interscience Publication, New York, 1985, Yoshimura, Bonding, Vol. 29, No. 12, 32, 1985, Yoshimura, Bonding, Volume 30, No. 5, 42, 1986, Yoshimura, Bonding, Volume 30, No. 7, 42, 1986, JP-A-11-100378, Patent No. 2906245, Patent No. 2926262, etc. Can be synthesized.

The second polymerizable compound has a functional group having hydrogen bonding property in the molecule, and has a polymerizable group capable of polymerizing reaction with the first polymerizable compound.
As a functional group which has hydrogen bondability, a urethane group, a urea group, or a hydroxyl group etc. are mentioned.
As the polymerizable group capable of polymerizing reaction with the first polymerizable compound, for example, when the first polymerizable compound is a bifunctional or more (meth) acrylate monomer, it may be a (meth) acryloyl group, and When the polymerizable compound is a monomer having two or more functional groups selected from the group consisting of an epoxy group and an oxetanyl group, it may be an epoxy group or an oxetanyl group.

As the (meth) acrylate monomer containing a urethane group, diisocyanates such as TDI, MDI, HDI, IPDI, HMDI, etc. and poly (propylene oxide) diol, poly (tetramethylene oxide) diol, ethoxylated bisphenol A, ethoxylated bisphenol Reaction of S spiro glycol, caprolactone modified diol, polyol such as carbonate diol, and hydroxy acrylate such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidol di (meth) acrylate, pentaerythritol triacrylate Monomers and oligomers obtained by the reaction, as described in JP-A-2002-265650, JP-A-2002-355936, and JP-A-2002-06723. It can be mentioned polyfunctional urethane monomers described in JP-like. Specifically, adducts of TDI and hydroxyethyl acrylate, adducts of IPDI and hydroxyethyl acrylate, adducts of HDI and pentaerythritol triacrylate (PETA), and adducts of TDI and PETA remained. Compounds obtained by reacting isocyanate and dodecyloxyhydroxypropyl acrylate, adducts of 6,6 nylon and TDI, adducts of pentaerythritol, TDI and hydroxyethyl acrylate, and the like can be mentioned, but are not limited thereto. Absent.

Commercially available products that can be suitably used as the (meth) acrylate monomer containing a urethane group include AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, manufactured by Kyoeisha Chemical Co., Ltd. UF-8001G, DAUA-167, UA-160TM manufactured by Shin-Nakamura Chemical Co., Ltd., UV-4108F manufactured by Osaka Organic Chemical Industry Co., Ltd., UV-4117F, etc. may be mentioned. These can be used singly or in combination of two or more.

As a (meth) acrylate monomer containing a hydroxyl group, the compound synthesize | combined by reaction of the compound which has an epoxy group, and (meth) acrylic acid can be mentioned. Representative ones are classified into bisphenol A type, bisphenol S type, bisphenol F type, epoxidized oil type, phenol novolak type and alicyclic type according to the compound having an epoxy group. As a specific example, (meth) acrylate obtained by reacting (meth) acrylic acid with an adduct of bisphenol A and epichlorohydrin, and epichlorohydrin with phenol novolak reacted with (meth) acrylic acid ( (Meth) acrylate, (meth) acrylate obtained by reacting (meth) acrylic acid with an adduct of bisphenol S and epichlorohydrin, and (meth) acrylic acid with an adduct of bisphenol S and epichlorohydrin ( Mention may be made of (meth) acrylates, (meth) acrylates obtained by reacting (meth) acrylic acid with epoxidized soybean oil, and the like. Moreover, as a (meth) acrylate monomer containing a hydroxyl group, although the (meth) acrylate monomer etc. which have a carboxy group or a phosphoric acid group at the terminal can be mentioned, it is not limited to these.

Commercial products that can be suitably used as the second polymerizable compound containing a hydroxyl group include epoxy esters manufactured by Kyoeisha Chemical Co., Ltd., M-600A, 40 EM, 70 PA, 200 PA, 80 MFA, 300 M, 3002 A, 3000 MK, 3000 A, 4-hydroxybutyl acrylate manufactured by Nippon Kasei Co., Ltd., monofunctional acrylate A-SA manufactured by Shin-Nakamura Chemical Co., Ltd., monofunctional methacrylate SA, monofunctional acrylate β-carboxyethyl acrylate manufactured by Daicel Ornex Co., Ltd. And JPA-514 manufactured by Johoku Chemical Industry Co., Ltd. These can be used singly or in combination of two or more.
The mass ratio of the first polymerizable compound to the second polymerizable compound may be 10:90 to 99: 1, preferably 10:90 to 90:10. It is also preferable that the content of the first polymerizable compound is larger than the content of the second polymerizable compound, specifically, (content of the first polymerizable compound) / (second polymerizable compound) The content is preferably 2 to 10.

When a resin containing a first polymerizable compound and a second polymerizable compound is used as a matrix, it is preferable that the matrix further contains a monofunctional (meth) acrylate monomer. As a monofunctional (meth) acrylate monomer, acrylic acid and methacrylic acid, derivatives thereof, more specifically, monomers having one polymerizable unsaturated bond ((meth) acryloyl group) of (meth) acrylic acid in the molecule Can be mentioned. Although the compound is mentioned to the following as those specific examples, this invention is not limited to this.
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 1 to 30 carbon atoms in the alkyl group such as meta) acrylate; aralkyl (meth) acrylates having 7 to 20 carbon atoms in the aralkyl group such as benzyl (meth) acrylate; butoxyethyl (meth) acrylate ) Alkoxyalkyl (meth) acrylates having 2 to 30 carbon atoms in the alkoxyalkyl group such as acrylate; total carbon number of (monoalkyl or dialkyl) aminoalkyl groups such as N, N-dimethylaminoethyl (meth) acrylate 1 to 2 Aminoalkyl (meth) acrylates; (meth) acrylates of diethylene glycol ethyl ether, (meth) acrylates of triethylene glycol butyl ether, (meth) acrylates of tetraethylene glycol monomethyl ether, (meth) acrylates of hexaethylene glycol monomethyl ether, Monomethyl ether (meth) acrylate of octaethylene glycol, monomethyl ether (meth) acrylate of nona ethylene glycol, monomethyl ether (meth) acrylate of dipropylene glycol, monomethyl ether (meth) acrylate of heptapropylene glycol, monoethyl of tetraethylene glycol A terminal alkyl group having 1 to 10 carbon atoms in an alkylene chain such as ether (meth) acrylate (Meth) acrylate of polyalkylene glycol alkyl ether having 1 to 10 carbon atoms of ether; 1 to 30 carbon atoms of alkylene chain such as (meth) acrylate of hexaethylene glycol phenyl ether and 6 carbon atoms of terminal aryl ether (Meth) acrylates of polyalkylene glycol aryl ethers of to 20; alicyclic structures such as cyclohexyl (meth) acrylates, dicyclopentanyl (meth) acrylates, isobornyl (meth) acrylates, methylene oxide-added cyclodecatriene (meth) acrylates, etc. (Meth) acrylates having 4 to 30 carbon atoms in total; fluorinated alkyl (meth) acrylates 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) acrylates having hydroxyl groups such as (meth) acrylates, glycerol mono or di (meth) acrylates; (meth) acrylates having glycidyl groups such as glycidyl (meth) acrylates; tetraethylene glycol mono (meth) acrylates, hexa Polyethylene glycol mono (meth) ene having 1 to 30 carbon atoms in the alkylene chain, such as ethylene glycol mono (meth) acrylate, octapropylene glycol mono (meth) acrylate, etc. ) Acrylate; (meth) acrylamide, N, N- dimethyl (meth) acrylamide, N- isopropyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide, acryloyl morpholine (meth) acrylamide and the like.
The monofunctional (meth) acrylate monomer is preferably contained in an amount of 1 to 300 parts by mass, preferably 50 to 150 parts by mass, per 100 parts by mass of the total mass of the first polymerizable compound and the second polymerizable compound. More preferably, it is included.

In addition, it is preferable to include a compound having a long chain alkyl group having 4 to 30 carbon atoms. Specifically, it is preferable that at least one of the first polymerizable compound, the second polymerizable compound, and the monofunctional (meth) acrylate monomer have a long-chain alkyl group having 4 to 30 carbon atoms. The long chain alkyl group is more preferably a long chain alkyl group having 12 to 22 carbon atoms. This is because the dispersibility of the quantum dot is improved. As the dispersibility of the quantum dots is improved, the amount of light orthogonal to the light conversion layer from the light conversion layer is increased, which is effective to improve the front luminance and the front contrast.
Specific examples of the monofunctional (meth) acrylate monomer having a long-chain alkyl group having 4 to 30 carbon atoms include butyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate and 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, etc. preferable. Among these, lauryl (meth) acrylate, oleyl (meth) acrylate and stearyl (meth) acrylate are particularly preferable.

Moreover, in resin which becomes a matrix, trifluoroethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, (perfluorobutyl) ethyl (meth) acrylate, perfluorobutyl-hydroxypropyl (meth) acrylate, (perfluoro (perfluoro) A compound having a fluorine atom such as hexyl) ethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate and the like may be included. Coating property can be improved by containing these compounds.
Further, the total amount of resin to be a matrix in the quantum dot layer is not particularly limited, but it is preferably 90 to 99.9 parts by mass, and 92 to 99 parts by mass with respect to 100 parts by mass of the quantum dot layer. It is more preferable that it is a part.

The thickness of the quantum dot layer is not particularly limited, but is preferably 5 μm to 200 μm, and more preferably 10 μm to 150 μm in terms of handleability and light emission characteristics.
The above thickness is intended to be an average thickness, and the average thickness is calculated by measuring the thickness of any 10 points or more of any 10 points or more in the region 10 mm from the end face of the quantum dot layer. Find on average.
Further, it is preferable that the thickness of the region other than the squeeze region of the functional layer 12, that is, the inner side of the squeeze region is in the range of ± 2% of the above-mentioned average thickness. By setting the thickness of the area other than the aperture area to a flat thickness of ± 2%, the variation in the luminance of the light emitted from the functional layer is suppressed, and the light emission distribution of the emitted light, for example, blue light, It is preferable in that the emission distribution of red light and green light can be made uniform, and the performance can be stabilized.

There is no limitation in particular in the formation method of a quantum dot layer, What is necessary is just to form by a well-known method. For example, it can be formed by preparing a coating composition in which quantum dots, a resin serving as a matrix, and a solvent are mixed, and coating the coating composition on the gas barrier film 14 and curing it by UV irradiation or the like.
In addition, you may add a polymerization initiator, a silane coupling agent, etc. to the coating composition used as a quantum dot layer as needed.

The gas barrier film 14 is a film having gas barrier properties, which is laminated on the main surface of the functional layer 12. That is, the gas barrier film 14 is a member for covering the main surface of the functional layer 12 and suppressing the infiltration of moisture and oxygen from the main surface of the functional layer 12.

The gas barrier film 14 preferably has a water vapor transmission rate of 1 × 10 ⁻³ [g / (m ² · day)] or less.
Further, the gas barrier film 14 preferably has an oxygen permeability of 1 × 10 ⁻² [cc / (m ² · day · atm)] or less.
By using a gas barrier film 14 having low water vapor permeability and low oxygen permeability, that is, high gas barrier properties, it is possible to prevent moisture and oxygen from entering the functional layer 12 and to prevent deterioration of the functional layer 12 more suitably. Can.
The water vapor transmission rate was measured by Mocon method. In addition, when the water vapor transmission rate exceeds the measurement limit of Mocon method, it is measured by the calcium corrosion method (the method described in JP-A-2005-283561).
In addition, the oxygen permeability was measured under the conditions of a temperature of 40 ° C. and a humidity of 90% RH using a measuring apparatus (manufactured by Nippon AI Co., Ltd.) by an APIMS method (atmospheric pressure ionization mass spectrometry).

The thickness of the gas barrier film 14 is preferably 5 μm to 100 μm, more preferably 10 μm to 70 μm, and particularly preferably 15 μm to 55 μm.
By setting the thickness of the gas barrier film 14 to 100 μm or less, sufficient flexibility can be given, and the thickness of the end face of the functional layer 12 is reduced while narrowing the width of the squeeze area at the end described later can do. Moreover, it is preferable also in the point which can make thickness of the functional laminated film 10 whole thin.
Moreover, when forming the functional layer 12 between two gas barrier films 14 by making the thickness of the gas barrier film 14 into 5 micrometers or more, it is preferable at the point which can make the thickness of the functional layer 12 uniform.

Moreover, it is preferable that the gas barrier film 14 has flexibility that can exhibit gas barrier properties without cracking of the inorganic layer 26 described later even after being stretched by 2.5%.
Specifically, the water vapor transmission rate after the gas barrier film 14 is stretched 2.5% in the plane direction is preferably 1 × 10 ⁻³ [g / (m ² · day)] or less. Similarly, the oxygen permeability after stretching the gas barrier film in the plane direction by 2.5% is also preferably 1 × 10 ⁻² [cc / (m ² · day · atm)] or less.
Even if the gas barrier film 14 is stretched by 2.5% in the planar direction, the width of the throttling region of the end portion described later is obtained by having sufficient flexibility such that the gas barrier properties such as water vapor permeability and oxygen permeability do not decrease. While narrowing, the thickness of the end face of the functional layer 12 can be reduced.

Here, as the gas barrier film 14, one having at least one organic layer and at least one inorganic layer as the gas barrier layer 22 on the gas barrier support 20 is suitably used.
In FIG. 2, sectional drawing which represents an example of a gas barrier film notionally is shown.
The gas barrier film 14 shown in FIG. 2 has a gas barrier layer 22 having an inorganic layer 26 and an organic layer 24 and a gas barrier support 20 for supporting the gas barrier layer 22.

The gas barrier film 14 only needs to have at least one inorganic layer 26 on the gas barrier support 20, and one combination of the inorganic layer 26 and the organic layer 24 serving as the base of the inorganic layer 26 is required. It is preferable to have the above. Therefore, the gas barrier film 14 may have two combinations of the inorganic layer 26 and the organic layer 24 of the base, or may have three or more. The organic layer 24 acts as a base layer for properly forming the inorganic layer 26. The larger the number of combinations of the combination of the base organic layer 24 and the inorganic layer 26, the better the gas barrier properties. A gas barrier film can be obtained.

The outermost surface of the gas barrier film 14 is preferably the inorganic layer 26, and the functional layer 12 is preferably laminated on the inorganic layer 26 side.
By forming the outermost surface of the gas barrier film 14 as the inorganic layer 26, even if outgas is released from the gas barrier support 20 or the organic layer 24, the outgas is shielded by the inorganic layer 26 and can be prevented from reaching the functional layer 12 .

As the gas barrier support 20 of the gas barrier film 14, various known gas barrier films used as a support can be used.
Among them, films made of various plastics (polymer material / resin material) are suitably used in terms of easy thinning and weight reduction and being suitable for flexibility.
Specifically, polyethylene (PE), polyethylene naphthalate (PEN), polyamide (PA), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polyvinyl alcohol (PVA), polyacritonitrile (PAN), polyimide ( PI), transparent polyimide, polymethyl methacrylate resin (PMMA), polycarbonate (PC), polyacrylate, polymethacrylate, polypropylene (PP), polystyrene (PS), ABS, cyclic olefin copolymer (COC), cycloolefin polymer ( Plastic films made of COP) and triacetyl cellulose (TAC) are suitably exemplified.

Here, as the material of the gas barrier support 20, it is preferable to use a material having a melting point of 230 ° C. or less and a glass transition temperature of 120 ° C. or less.
By using a material having a melting point of 230 ° C. or less and a glass transition temperature of 120 ° C. or less as the material of the gas barrier support 20, the laminate of the functional layer 12 and the gas barrier film 14 is cut in the cutting step described later When the thickness of the functional layer is made smaller than the average thickness in the range of 10 mm or less from the surface to form the throttling area, the throttling area can be formed more easily by heating the blade.

Moreover, it is preferable that the gas barrier support 20 has a high transmittance of ultraviolet light. As a method of forming the functional layer 12 such as a quantum dot layer, a coating composition to be the functional layer 12 is formed on the gas barrier film 14, and further, after the gas barrier film 14 is laminated on the coating film, ultraviolet rays are irradiated. A method of curing the coating film to form the functional layer 12 is suitably used. Therefore, it is preferable that the gas barrier support 20 sufficiently transmit ultraviolet light for irradiating the functional layer 12.

As a material of the gas barrier support 20, PET, COP, PC, PI, TAC, etc. are more preferably used from the viewpoints of melting point, glass transition temperature, and ultraviolet light transmittance.

The thickness of the gas barrier support 20 may be appropriately set depending on the application and size. Here, according to the study of the present inventor, the thickness of the gas barrier support 20 is preferably about 5 μm to 100 μm. By setting the thickness of the gas barrier support 20 in this range, preferable results can be obtained in terms of weight reduction, thinning, flexibility, and the like.
The gas barrier support 20 may be provided with functions such as reflection prevention, retardation control, and light extraction efficiency improvement on the surface of such a plastic film.

The gas barrier layer 22 has an inorganic layer 26 mainly exhibiting gas barrier properties, and an organic layer 24 to be a base layer of the inorganic layer 26.

The organic layer 24 is to be a base layer of the inorganic layer 26 that mainly exhibits gas barrier properties in the gas barrier film 14.
As the organic layer 24, various known gas barrier films used as the organic layer 24 can be used. For example, the organic layer 24 is a film containing an organic compound as a main component, and basically, one formed by crosslinking a monomer and / or an oligomer can be used.
Note that the film containing an organic compound as a main component is a film containing 50% or more of an organic compound.

The gas barrier film 14 also functions as a cushion of the inorganic layer 26 by having the organic layer 24 to be the base. Therefore, when the inorganic layer 26 receives an impact from the outside during the cutting process to be described later, damage to the inorganic layer 26 can be prevented by the cushioning effect of the organic layer 24.
Thereby, in the functional laminated film 10, the gas barrier film 14 appropriately exhibits the gas barrier performance, and the deterioration of the functional layer 12 due to water or oxygen can be suitably prevented.

In addition, the gas barrier film 14 includes the organic layer 24 serving as the base of the inorganic layer 26, thereby embedding the irregularities on the surface of the gas barrier support 20, foreign substances adhering to the surface, etc. The film formation surface can be made appropriate. As a result, it is possible to form an appropriate inorganic layer 26 without any gap and without cracks, cracks and the like on the entire surface of the film formation surface. Thereby, a high gas barrier performance can be obtained such that the water vapor transmission rate is 1 × 10 ⁻³ [g / (m ² · day)] or less.

In the gas barrier film 14, various organic compounds (resin / polymer compound) can be used as a material for forming the organic layer 24.
Specifically, polyester, acrylic resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluorine resin, polyimide, fluorinated polyimide, polyamide, polyamide imide, polyether imide, cellulose acylate, polyurethane, poly Thermoplastic resins such as ether ether ketone, polycarbonate, alicyclic polyolefin, polyarylate, polyether sulfone, polysulfone, fluorene ring modified polycarbonate, alicyclic modified polycarbonate, fluorene ring modified polyester, acryloyl compound, etc. or polysiloxane, other A film of an organosilicon compound is preferably exemplified. A plurality of these may be used in combination.

Among them, the organic layer 24 composed of a radically polymerizable compound and / or a polymer of a cationically polymerizable compound having an ether group as a functional group is preferable in terms of excellent glass transition temperature and strength.
Among them, particularly, in addition to the above-mentioned strength, in view of low refractive index, high transparency, and excellent optical characteristics, etc., a glass transition temperature of 120 ° C. is mainly composed of acrylate and / or methacrylate monomer or oligomer polymer. The above acrylic resin and methacrylic resin are suitably exemplified as the organic layer 24.
Among them, bifunctional or more, particularly trifunctional or more, such as dipropylene glycol di (meth) acrylate (DPGDA), trimethylolpropane tri (meth) acrylate (TMPTA) and dipentaerythritol hexa (meth) acrylate (DPHA). The acrylic resin and methacrylic resin which have as a main component the polymer of the monomer and oligomer of the acrylate and / or the methacrylate of these are illustrated suitably. It is also preferable to use a plurality of these acrylic resins and methacrylic resins.
By forming the organic layer 24 with such an acrylic resin or methacrylic resin, the inorganic layer 26 can be formed on the base having a firm skeleton, so that the inorganic layer 26 can be formed more densely and has high gas barrier properties. .

The thickness of the organic layer 24 is preferably 0.5 μm to 5 μm.
By setting the thickness of the organic layer 24 to 0.5 μm or more, the effect as a cushion is sufficiently exerted when the inorganic layer 26 receives an impact from the outside in the cutting step to be described later, etc. Damage to the layer 26 can be prevented more reliably. Further, by setting the thickness of the organic layer 24 to 1 μm or more, the film-forming surface of the inorganic layer 26 is more suitably made appropriate, and the appropriate inorganic layer 26 free from cracks, cracks and the like is provided all over the film-forming surface. The film can be formed across.
Further, by setting the thickness of the organic layer 24 to 5 μm or less, the occurrence of problems such as cracking of the organic layer 24 and curling of the gas barrier film 14 due to the organic layer 24 being too thick is suitably prevented. be able to.
In consideration of the above points, the thickness of the organic layer 24 is more preferably 1 μm to 5 μm.

When the gas barrier film has a plurality of organic layers, the thickness of each organic layer may be the same or different.
Moreover, when it has multiple organic layers, the forming material of each organic layer may be same or different. However, in terms of productivity and the like, it is preferable to form all the organic layers of the same material.

The organic layer 24 may be formed by a known method such as a coating method or flash evaporation.
Further, in order to improve the adhesion to the inorganic layer 26 which is the lower layer of the organic layer 24, the organic layer 24 preferably contains a silane coupling agent.

An inorganic layer 26 is formed on the organic layer 24 with the organic layer 24 as a base.
The inorganic layer 26 is a film containing an inorganic compound as a main component, and the gas barrier film 14 mainly exhibits gas barrier properties.

The formation material of the inorganic layer 26 contains silicon nitride as a main component.
By using silicon nitride as a material for forming the inorganic layer 26, it is possible to exhibit high transparency, excellent gas barrier properties, and further, excellent flexibility. Therefore, even if the thickness of the end face of the functional layer 12 is reduced while narrowing the width of the squeeze area at the end described later, the inorganic layer 26 does not break, and sufficient gas barrier properties can be exhibited.

Here, in the inorganic layer 26, ie, the silicon nitride film as a gas barrier film, the hydrogen content in the film is preferably 10 atomic% to 30 atomic%.
When the hydrogen content of the inorganic layer 26 is 30 atomic% or less, sufficient oxidation resistance can be exhibited, and sufficient gas barrier properties can be ensured for a long time. Therefore, it is possible to prevent the inconvenience such as the inorganic layer 26 becoming easily broken with time.
In addition, by setting the hydrogen content of the inorganic layer 26 to 10 atomic% or more, it is possible to improve the flexibility by reducing the three-dimensional bonding between the bonds in the film very strongly.
In the silicon nitride film, hydrogen is contained in the source gas or the like and is inevitably mixed. In order to reduce the hydrogen content, processing and operations therefor (for example, raising the temperature of the substrate during film formation, post-annealing treatment, and the like) are necessary, and the production cost also increases. Therefore, by setting the hydrogen content in the inorganic layer 26 to 10 atomic% or more, suitable productivity can be secured.
Further, from the above viewpoint, the hydrogen content in the inorganic layer 26 is more preferably 15 atomic% to 25 atomic%.

Here, the hydrogen content in the inorganic layer 26 in the present invention is a value measured by a Rutherford backscattering analysis method and a hydrogen forward scattering analysis method using a backscattering measurement apparatus (an AN2500 manufactured by Nisshin High Voltages Co., Ltd.) .

In addition, the inorganic layer 26 has a peak intensity of absorption due to stretching vibration of Si—H whose peak is located in 2170 cm ⁻¹ to 2200 cm ⁻¹ in a Fourier transform infrared absorption spectrum (hereinafter referred to as FTIR) of a silicon nitride film. The intensity ratio of I (Si-H) to the peak intensity I (Si-N) of absorption due to stretching vibration of Si-N near 840 cm ^-1 [I (Si-H) / I (Si-N) ] Is preferably 0.03 to 0.15.
By setting the peak intensity ratio to 0.03 to 0.15, sufficient oxidation resistance can be obtained, sufficient gas barrier properties can be ensured for a long time, and sufficient flexibility can be obtained.

Further, the peak intensity I (N−H) of absorption due to stretching vibration of NH in the vicinity of 3350 cm ⁻¹ in the FTIR of the inorganic layer 26 and the peak intensity I of absorption due to stretching vibration of Si—N near 840 cm ⁻¹ It is preferable that the intensity ratio [I (NH) / I (Si-N)] to Si-N) is 0.03 to 0.07, and it is 0.03 to 0.06. Is more preferred.
By setting the peak intensity ratio [I (N−H) / I (Si−N)] to 0.03 or more, the coloring of the film can be more suitably suppressed to obtain the inorganic layer 26 with high transparency. Favorable results are obtained in that the adhesion with the gas barrier support 20 and the organic layer 24 to be the lower layer can be improved. Further, by setting the peak intensity ratio [I (NH) / I (Si-N)] to 0.07 or less, higher oxidation resistance can be ensured, and sufficient gas barrier properties can be ensured over a long period of time. Favorable results can be obtained in that the adhesion with the gas barrier support 20 and the organic layer 24 can be improved, and sufficient flexibility can be easily obtained.

Here, in the measurement of the FTIR of the inorganic layer 26 in the present invention, the infrared absorption spectrum of the surface of the gas barrier film is measured using an ATR (Attenuated Total Reflectance) mode with an FTIR measurement device, and the organic layer is formed as a reference The infrared absorption spectrum of the surface was measured with the obtained film as a baseline, and the infrared absorption spectrum of the inorganic layer was determined from the difference.

In the present invention, the film density of the inorganic layer 26 is not particularly limited, but is preferably 2.1 g / cm ³ to 2.7 g / cm ³ .
By setting the film density to 2.1 g / cm ³ or more, higher oxidation resistance can be ensured, sufficient gas barrier properties can be ensured over a long period, adhesion to the substrate Z and the lower layer can be improved, etc. Give favorable results. In addition, when the film density is high, the film tends to be easily broken. However, by setting the film density to 2.7 g / cm ³ or less, it is possible to suitably prevent the crack caused by the high film density. Favorable results are obtained in that the flexibility can be improved and the adhesion to the substrate Z and the lower layer can be improved.
The film density of the inorganic layer 26 is more preferably 2.3 g / cm ³ to 2.6 g / cm ³ because the above advantages can be obtained more preferably.

Here, the film density of the inorganic layer 26 in the present invention is a value measured by an X-ray reflectance measurement method using a thin film X-ray diffractometer (ATX-E manufactured by Rigaku Corporation).

When the gas barrier film has a plurality of inorganic layers, the materials for forming the inorganic layers may be different from each other. However, in consideration of productivity and the like, it is preferable to form all the inorganic layers with the same material.

The thickness of the inorganic layer 26 may be appropriately determined according to the material to be formed, so as to express the desired gas barrier properties. According to the study of the present inventor, the thickness of the inorganic layer 26 is preferably 10 to 200 nm.
By setting the thickness of the inorganic layer 26 to 10 nm or more, the inorganic layer 26 that stably exhibits sufficient gas barrier performance can be formed. In addition, the inorganic layer 26 is generally brittle, and if it is too thick, there is a possibility that cracking, cracks, peeling, etc. may occur. However, when the thickness of the inorganic layer 26 is 200 nm or less, cracking may occur. It can prevent and improve flexibility.
Further, in consideration of such a point, the thickness of the inorganic layer 26 is preferably 10 nm to 100 nm, and particularly preferably 15 nm to 75 nm.
When the gas barrier film has a plurality of inorganic layers, the thickness of each inorganic layer may be the same or different.

The inorganic layer 26 may be formed by a known method of forming a silicon nitride film. Specifically, vapor deposition methods such as plasma CVD such as CCP-CVD and ICP-CVD, sputtering such as magnetron sputtering and reactive sputtering, and vacuum deposition are suitably exemplified.

Next, the aperture area will be described in more detail with reference to FIG.
FIG. 3 is a cross-sectional view showing an end portion of the functional laminated film 10 shown in FIG. 1 in an enlarged manner.
As shown in FIG. 3, at the end portion (peripheral portion) of the functional laminate film 10, one gas barrier film 14 is bent in the direction approaching the other gas barrier film 14 side. That is, at the end, the gap between the gas barrier films 14 is narrowed so as to narrow toward the end face. Further, in FIG. 3, the end face of the functional layer 12 is open in the thickness H _1.
In other words, the gas barrier film 14 is an end portion such that the thickness H ₁ of the functional layer 12 at the end face is thinner than the thickness of the functional layer 12 at the central portion, that is, the average thickness H ₀ of the functional layer 12. It is arranged by being bent.

As described above, by reducing the gap between the gas barrier films 14 at the end, the surface area of the end face of the functional layer 12 is reduced to prevent the penetration of moisture, oxygen, etc. from the end face of the functional layer 12. Thus, deterioration of the functional layer 12 can be prevented.
As described above, the area having a thickness smaller than the average thickness of the functional layer 12 is referred to as a squeeze area. Specifically, an area which is thinner by 10% or more than the average thickness continuously from the end face is referred to as a throttling area.

Here, in the present invention, the width T from the end face of the throttle region is 10 mm or less.

As described above, the gas barrier film is used to protect a functional layer that is easily degraded by moisture or oxygen, such as a quantum dot layer, and to further suppress entry of moisture or oxygen from the end face of the functional layer. It has been proposed to seal the end face with a gas barrier film.
On the other hand, in the liquid crystal display device, in addition to the demand for further thinning, narrowing of the frame is required to increase the ratio of the display area to the entire display device.
Therefore, if the gas barrier film is narrowed to seal the end in order to reduce the infiltration of moisture or oxygen from the end of the functional layer, the thickness of the functional layer at the end becomes thinner. At the end of the layer, the function can not be sufficiently expressed, and the size of the area that can be effectively used may be reduced, and the frame portion may be enlarged.
Then, it is possible to make a frame part small and to enlarge an area which can be effectively used by forming so that thickness may become thin suddenly near the end face. However, since a barrier layer made of an oxide such as silicon oxide, titanium oxide, or aluminum oxide is hard and brittle, the barrier layer may have a barrier layer using such an oxide as a forming material. As a result, there is a problem that the gas barrier property is lowered and it is not possible to suppress the entry of water or oxygen into the functional layer.

On the other hand, in the present invention, silicon nitride is used as the inorganic layer 26 that exhibits gas barrier properties, and the width T from the end face of the narrowed region where the thickness of the functional layer 12 is reduced is 10 mm or less Have. Thereby, the end of the functional laminated film 10 is squeezed, the surface area of the end face of the functional layer 12 is reduced, and when intrusion of moisture, oxygen, etc. from the end face is suppressed, the end face is sharply curved near the end face Even when the position to start squeezing is 10 mm or less from the end face, the inorganic layer is not easily broken, so that sufficient gas barrier properties can be maintained. Therefore, it is possible to suppress the infiltration of moisture or oxygen from the end face of the functional layer 12 to prevent the deterioration of the functional layer 12, and the functional layer 12 can not sufficiently exhibit its function without reducing the gas barrier properties. By reducing the area, the ratio of the area that can be effectively used as the functional layer 12 can be increased, and the frame can be narrowed.

Here, the width T of the narrowed region from the end face is preferably 1 mm or less, and more preferably 0.2 mm or less.
By narrowing the width T from the end face of the throttling region, the frame can be further narrowed. In the present invention, since silicon nitride is used as the inorganic layer 26, sufficient gas barrier properties can be exhibited without cracking of the inorganic layer even if the frame is thus narrowed.

The thickness H ₁ at the end face of the functional layer 12 is preferably 50% or less of the average thickness H ₀ of the functional layer 12, and more preferably 10% or less.
By making thickness H ₁ in the end face of functional layer 12 50% or less of average thickness H ₀ or less, more preferably 10% or less, penetration of moisture and oxygen from the end face of functional layer 12 is more suitably reduced can do. Further, in the present invention, since silicon nitride is used as the inorganic layer 26, even if the thickness H _{1 of the} end face is narrowed to be smaller than the average thickness H ₀ as described above, the inorganic layer is cracked. Sufficient gas barrier properties can be expressed without.

Furthermore, as in the functional laminated film shown in FIG. 4, the thickness H ₁ at the end face of the inorganic layer 26 may be 0 mm, that is, the end may be narrowed so that the gas barrier films 14 are in contact with each other. Thereby, the penetration of moisture and oxygen from the end face of the functional layer 12 can be more suitably prevented.

Moreover, in the example shown in FIG. 3, although it was set as the structure which makes thickness H ₁ of the end surface of the functional layer 12 thin by curving one gas barrier film 14, limitation is not carried out to this, The end portions may be curved toward the functional layer 12 to reduce the thickness H ₁ of the end surface of the functional layer 12.

In addition, although it was set as the structure which laminated | stacked three layers, the gas barrier film 14, the functional layer 12, and the gas barrier film 14, as shown in FIG. 1, the present invention is not limited to this, Other It may have a layer. For example, it may have a hard coat layer, an optical compensation layer, a transparent conductive layer, and the like.

Next, the method for producing the functional laminated film of the present invention (hereinafter, also referred to as “the method for producing the present invention”) will be described using FIGS. 5 (A) to 5 (C).
The production method of the present invention is
Preparing a laminate having a functional layer, and two gas barrier films having an inorganic layer containing silicon nitride, which are respectively laminated on one principal surface and the other principal surface of the functional layer;
Cutting the laminate to form a thickness of the functional layer in a range of 10 mm or less from the cut surface, thinner than the average thickness of the functional layer, and the thinnest on the cut surface. It is a manufacturing method of a functional lamination film.

In the preparation step, as shown in FIG. 5A, a laminate 30 in which the gas barrier film 14 is laminated on both sides of the functional layer 12 is prepared.
There is no particular limitation on the method for producing such a laminate 30, and as described above, the coating composition to be the functional layer 12 is formed on the gas barrier film 14, and the gas barrier film 14 is further laminated on the coating film. A method of producing the laminate 30 by irradiating the ultraviolet rays and curing the coating film to form the functional layer 12 can be suitably used.

Next, in the cutting step, as shown in FIG. 5 (B), the laminated body 30 is cut at a predetermined position using a blade v. At this time, the vicinity of the cutting portion is compressed by the pressing by the blade v. Thereby, as shown in FIG. 5C, the thickness of the functional layer 12 in the range of 10 mm or less from the cut surface is thinner than the average thickness of the functional layer 12, and the thickness at the cut surface is the most It is formed to be thinner.

In the manufacturing method of the present invention, since the thickness of the functional layer 12 in the vicinity of the cut surface is formed thin by cutting the laminate 30 in this manner, the gas barrier film is sharply curved in the vicinity of the cut surface. The thickness of the functional layer 12 can be thin in a narrow range of 10 mm or less from the cut surface. In addition, it is possible to reduce the occurrence of foreign matter such as burrs and chips that degrade the quality of products and the occurrence of dimensional abnormalities.

Here, in the cutting step, it is preferable to use a metal blade v, and cutting is preferably performed by heating the temperature of the blade to the range of the glass transition temperature + 50 ° C. to the melting point + 50 ° C. of the gas barrier support 20.
By setting the temperature of the blade used for cutting in the above range, the gas barrier support 20 is easily heated and deformed at the cutting portion, and when cutting, the thickness of the functional layer 12 near the cutting portion is more suitably It can be formed thin. Moreover, the thickness of the functional layer 12 in a cut surface can be adjusted by adjusting the temperature of a blade.
Therefore, when the blade is heated for cutting, it is preferable to use a thermoplastic resin as the gas barrier support 20.

The functional layer 12 such as a quantum dot layer may be weak to heat. Therefore, when the laminate 30 itself is heated, the functional layer may be degraded, and a predetermined function may not be realized.
On the other hand, in the manufacturing method of the present invention, by heating the blade, the gas barrier support 20 is softened while the deterioration of the quantum dot layer is prevented, and the thickness of the functional layer 12 near the cut portion is thin. It can be formed.

Moreover, there is no limitation in particular also in the method to heat a blade, and it may heat using well-known heaters, such as an electric heater and an induction heater.

There is no limitation in particular in the cutter used in a cutting process, Various known cutters can be utilized suitably.
For example, a slitter which is used for die cutting etc., a Thomson blade type in which a blade is bent in a frame shape and embedded in a base such as a plywood or resin plate, a cutting blade, or a slitter having a smooth blade on the outer periphery of a steel disc. A cutting method using a die cutter which is fixed to the outer peripheral surface of one roll of a blade and a roller pair and passes an object to be cut between the roller pair to perform contour processing is preferably available.
Moreover, the cutter used for cutting may be a double-edged blade or a single-edged blade.
Further, there is no particular limitation on the cutting edge angle of the cutting tool, and by appropriately selecting the cutting edge angle, it is possible to more suitably adjust the shape of the stop area such as the thickness of the end face. Preferably, the cutting edge angle is 20 to 40 °.

When cutting with a Thomson blade, a cutting blade or the like, the cutting speed is preferably 0.01 mm / s to 100 mm / s, and more preferably 0.1 mm / s to 10 mm / s.
Usually, in the cutting of a film-like material, the cutting speed is about 100 mm / s to 1000 mm / s from the viewpoint of productivity etc. However, in the present invention, the cutting speed is 100 mm / s or less. The thickness of the functional layer can be more suitably reduced in the range of 10 mm or less from the cut surface. Further, in order to make the cutting speed less than 0.01 mm / s, it is difficult to control and the equipment becomes expensive, so it is preferable to set it to 0.01 mm / s or more.

In the cutting step, the long laminate may be cut in a predetermined shape to be the functional laminated film 10 while being conveyed in the longitudinal direction.
At that time, the cutting may be performed while conveying the long laminate in the longitudinal direction, or the conveyance and the cutting may be alternately performed intermittently.

As mentioned above, although the functional laminated film of this invention and its manufacturing method were demonstrated in detail, this invention is not limited to the said Example, In the range which does not deviate from the summary of this invention, various improvement and change are performed. Of course it is good.

Hereinafter, the present invention will be described in more detail by way of specific examples of the present invention.

Example 1
As Example 1, the functional laminated film 10 shown in FIG. 1 was produced.

<Functional laminated film>
[Preparation Process of Protective Film-Coated Laminate]
(Gas barrier film)
As the gas barrier film 14, a gas barrier film in which the organic layer 24 and the inorganic layer 26 were formed on the gas barrier support 20 was used.
As the gas barrier support 20, a polyethylene terephthalate film (PET film, Cosmo Shine A4300 manufactured by Toyobo Co., Ltd.) having a thickness of 50 μm, a width of 1000 mm, and a length of 100 m was used.
The gas barrier support has a melting point of 200 ° C. and a glass transition temperature of 80 ° C.

Next, the organic layer 24 was formed on the surface of the gas barrier support 20. The material of the organic layer 24 was coated on the gas barrier support 20 by a coating method, dried, and then irradiated with ultraviolet rays to perform polymerization, thereby forming a film having a thickness of 1 μm.
As a coating solution for forming the organic layer 24, the mass ratio of the polymerizable compound TMPTA (manufactured by Daicel Cytech Co., Ltd.) and the ultraviolet polymerization initiator (manufactured by Lamberti, ESACURE KTO 46) at a weight ratio of 95: 5 It weighed so that it became and these were dissolved in methyl ethyl ketone, and the coating liquid of 15% of solid content concentration was prepared.
The prepared polymerizable composition is applied onto the gas barrier support 20 by roll-to-roll (hereinafter also referred to as “RtoR”) using a die coater, passed through a drying zone at 50 ° C. for 3 minutes, and then UV light the irradiated (integrated radiation, about 600 mJ / cm ²⁾ UV cured to form an organic layer 24.
In addition, PE (PAC2-30-T, manufactured by San-A Kaken Co., Ltd.) was attached as a protective film for an organic layer with a pass roll immediately after the formation of the organic layer 24, conveyed, and wound up.

Next, after peeling off the protective film for an organic layer by CCP (capacitively coupled plasma method) -CVD using a general RtoR film forming apparatus, an inorganic layer 26 having a thickness of 50 nm is formed on the organic layer 24. It formed.
As source gases, silane gas (SiH ₄ ), ammonia gas (NH ₃ ), nitrogen gas (N ₂ ) and hydrogen gas (H ₂ ) were used. The amount of gas supplied was 160 sccm for silane gas, 370 sccm for ammonia gas, 240 sccm for nitrogen gas, and 590 sccm for hydrogen gas. Moreover, the film-forming pressure was 40 Pa. That is, the inorganic layer 26 is a silicon nitride film.
The plasma excitation power was 2.5 kW at a frequency of 13.56 MHz.

As described above, the gas barrier film 14 was produced.
The water vapor permeability and the oxygen permeability of the produced gas barrier film 14 were measured by the Ca corrosion method, and the water vapor permeability at a temperature of 40 ° C. and a humidity of 90% RH was 1 × 10 ⁻⁴ [g / (m ² · day) ]Met. In addition, when the oxygen permeability was measured by APIMS method, the oxygen permeability at a temperature of 40 ° C. and a humidity of 90% RH was 1 × 10 ⁻³ [cc / (m ² · day · atm)].
In addition, a sample of the gas barrier film 14 having a width of 10 mm and a length of 150 mm is prepared, and the sample is pulled to an elongation of 2.5% with Tensilon (AGS-J-5kN manufactured by Shimadzu Corporation), and then the water vapor transmission rate and oxygen are obtained. The transmittance was measured and found to be 1 × 10 ⁻⁴ [g / (m ² · day)] and 1 × 10 ⁻³ [cc / (m ² · day · atm)], respectively.
Furthermore, when the crack of the inorganic layer was observed while giving the amount of elongation (displacement) of the sample, the amount of elongation (breaking elongation) when the inorganic layer was broken was 3.5%.
In addition, PE (PAC2-30-T, manufactured by San-Ai Kaken Co., Ltd.) was attached as a protective film for the inorganic layer with a film surface touch roll immediately after the formation of the inorganic layer 26, and was transported and wound up.

(Functional layer)
Next, the protective film for the inorganic layer was peeled off with a RtoR coating device, and then the coating composition was applied on the inorganic layer 26 of the gas barrier film 14 by a coating method.
As a coating composition of the functional layer 12, the following each component was mixed and the quantum dot dispersion liquid was prepared.

Quantum dot A (emission maximum: 520 nm) 0.1 parts by mass Quantum dot B (emission maximum: 630 nm) 0.01 parts by mass Monofunctional methacrylate (lauryl methacrylate) 70 parts by mass Bifunctional acrylate (dipropylene glycol di) Acrylate)
20 parts by mass trifunctional acrylate (trimethylolpropane triacrylate)
10 parts by mass Photopolymerization initiator: Irgacure 819 (manufactured by BASF) 1 part by mass Organically modified smectite (layered clay compound, aspect ratio 20, major axis 0.15 μm) 2.5 parts by mass

The coating composition was previously stirred for 10 minutes with a dissolver at 150 rpm for about 30 minutes and simultaneously subjected to ultrasonic degassing (the ultrasonic transmitter used is Bransonic 8800 manufactured by Bransonic 8800, and a plastic container is interposed with water) This solution was irradiated with an ultrasonic power of 280 W and a frequency of 40 kH). After that, the coating composition was prepared by carrying out a filtration treatment with a filter (PALL profile II, pore diameter 100 μm) with a filtration accuracy of 100 μm.
Coating was performed using a die coater.
Next, on the applied coating composition, the same gas barrier film 14 as described above was laminated with the inorganic layer 26 directed to the coating composition side.
Thereafter, ultraviolet rays are irradiated (total irradiation amount: approximately 300 mJ / cm ² ) to perform UV curing, thereby forming the functional layer 12 having a thickness of 70 μm, and a laminate 30 is produced.

[Cutting process]
Next, while conveying the manufactured laminated body 30 by RtoR, punching processing was performed to a size of 160 mm × 90 mm using a Thomson blade, and a functional laminated film 10 was manufactured.
The Thomson blade used was a double-edge Thomson blade with a blade angle of 40 °.
The temperature of the blade was 150 ° C., and the cutting speed was 5 mm / s.

The thickness H ₁ of the functional layer 12 at the end face of the produced functional laminated film 10 and the width T of the squeeze area are observed at three points by observing the shape of the cross section using a laser microscope (LEXT manufactured by Olympus Corporation) It measured and calculated each average value. The thickness H ₁ of the end face was 35 μm, that is, 50% of the average thickness of the functional layer, and the width T of the throttling region was 8.0 mm.

Example 2
In the cutting step, the functional laminated film 10 was produced in the same manner as in Example 1 except that the heating temperature of the blade was changed to 100 ° C. and the cutting speed was changed to 8 mm / s.
The thickness H ₁ of the end face of the functional layer 12 of the produced functional laminate film 10 was 50 μm (70% of the average thickness of the functional layer), and the width T of the squeeze area was 7.8 mm.
[Example 3]
In the cutting step, the functional laminated film 10 was produced in the same manner as in Example 1 except that the heating temperature of the blade was changed to 220 ° C. and the cutting speed was changed to 3 mm / s.
The thickness H ₁ of the end face of the functional layer 12 of the produced functional laminate film 10 was 7 μm (10% of the average thickness of the functional layer), and the width T of the squeeze area was 8.2 mm.

Example 4
In the cutting step, the functional laminated film 10 was produced in the same manner as in Example 1 except that the heating temperature of the blade was changed to 250 ° C. and the cutting speed was changed to 1 mm / s.
The thickness H ₁ of the end face of the functional layer 12 of the produced functional laminate film 10 is 0 μm, that is, the gas barrier films 14 are in contact with each other as shown in FIG. 4. Further, the width T of the throttling area was 8.1 mm.
[Example 5]
A functional laminate film 10 was produced in the same manner as in Example 1 except that the thickness of the gas barrier support was changed to 38 μm, and the cutting step was changed to a double-edged Thomson blade having a blade angle of 30 °.
The thickness H ₁ of the end face of the functional layer 12 of the produced functional laminate film 10 was 35 μm (50% of the average thickness of the functional layer), and the width T of the squeeze area was 1 mm. In addition, after the gas barrier film 14 was stretched and pulled to 2.5%, the water vapor transmission rate and the oxygen transmission rate were measured to be 1 × 10 ⁻⁴ [g / (m ² · day)] and 1 × 10 ^{−, respectively. It was 3} [cc / (m ² · day · atm)]. Moreover, the breaking elongation of the gas barrier film 14 was 4%.
[Example 6]
A functional laminate film 10 was produced in the same manner as in Example 1 except that the thickness of the gas barrier support was changed to 23 μm, and in the cutting step, it was changed to a double-edged Thomson blade with a blade angle of 20 °.
The thickness H ₁ of the end face of the functional layer 12 of the produced functional laminate film 10 was 35 μm (50% of the average thickness of the functional layer), and the width T of the squeeze area was 0.18 mm. In addition, after the gas barrier film 14 was stretched and pulled to 2.5%, the water vapor transmission rate and the oxygen transmission rate were measured to be 1 × 10 ⁻⁴ [g / (m ² · day)] and 1 × 10 ^{−, respectively. It was 3} [cc / (m ² · day · atm)]. The breaking elongation of the gas barrier film 14 was 4.5%.

Comparative Example 1
In the cutting step, a functional laminated film was produced in the same manner as in Example 1 except that cutting was performed using a CO ₂ laser.
The thickness H ₁ of the end face of the functional layer of the produced functional laminate film was 30 μm (100% of the average thickness of the functional layer).

Comparative Example 2
A functional laminate film 10 was produced in the same manner as in Example 1 except that an alumina film was used instead of the silicon nitride film as the inorganic layer of the gas barrier film.
The thickness H ₁ of the end face of the functional layer of the functional laminated film produced was 35 μm (50% of the average thickness of the functional layer), and the width T of the squeeze area was 8.1 mm.
Further, when the water vapor permeability and oxygen permeability of the gas barrier film were measured, they were 1 × 10 ^-4 [g / (m ² · day)] and 1 × 10 ^-3 [cc / (m ² · day · atm, respectively) )]Met. Furthermore, when the gas barrier film was stretched and pulled to 2.5%, the water vapor transmission rate and the oxygen transmission rate were measured to be 3 × 10 ⁻² [g / (m ² · day)] and 4 × 10 ^{−1, respectively.} It was [cc / (m ² · day · atm)]. Moreover, the breaking elongation of the gas barrier film was 1%.

The alumina film was formed by a general sputtering apparatus. Specifically, the gas barrier support on which the organic layer was formed was loaded into a general sputtering apparatus, and an inorganic sintered body formed of an alumina film was formed by DC magnetron sputtering using an alumina sintered body as a target. .

[Evaluation]
<Gas barrier test>
The gas barrier property test, that is, the durability test was performed on the functional laminated films of Examples 1 to 6 and Comparative Example 1 produced.
Specifically, the functional laminate film immediately after preparation and the functional laminate film after standing for 100 hours in an environment of temperature 60 ° C. and humidity 90% RH are incorporated into the following liquid crystal display device, and uneven brightness is obtained. It measured and gas barrier property was evaluated by the change of the luminance nonuniformity before and behind humidification.

First, a commercially available liquid crystal display device (Panasonic product name: THL42D2) is disassembled, a functional laminated film is added on the light guide plate on the side with the liquid crystal cell, and the backlight unit is changed to the following B narrow band backlight unit And manufactured a backlight unit and a liquid crystal display. The B narrow band backlight unit used is provided with a blue light emitting diode (Nichia B-LED: Blue, main wavelength 465 nm, half width 20 nm) as a light source.

Next, color unevenness was evaluated when the liquid crystal display was displayed in white. The luminance was measured with a luminance meter (SR3, manufactured by TOPCON) installed at a distance of 740 mm at five points at equal intervals except for both ends 50 mm in the diagonal direction on the front of the display device. The difference between the respective luminances measured at 10 points was calculated from the calculated average value, and the maximum value thereof was divided by the average luminance and the value represented as a percentage was regarded as luminance unevenness.

It evaluated as follows based on the difference of the luminance nonuniformity before and behind humidification which was measured.
A: 5% or less.
B: 5% or more and 10% or less.
C: 10% or more and 20% or less.
D: more than 20%.
The results are shown in Table 1 below.

As shown in Table 1 above, it can be seen that the functional laminate film of the present invention has higher gas barrier properties than the comparative example.
Moreover, when Example 1 and Comparative Example 2 are compared, in Example 1, since the silicon nitride film is used as the inorganic layer of the gas barrier film, the inorganic layer does not break even when the width T of the throttling region is 10 mm or less. It can be seen that sufficient gas barrier properties are developed. On the other hand, in Comparative Example 2, since the alumina film is used as the inorganic layer, it is understood that when the width T of the throttling region is 10 mm or less, the inorganic layer is broken and the gas barrier property is lowered. In other words, when an alumina film is used as the inorganic layer, the width T needs to be increased in order to prevent cracking of the inorganic layer, and the frame portion can not be made smaller.
Furthermore, it is understood that the gas barrier properties can be further improved by curving the end portion of the gas barrier film suddenly to thin the thickness of the end face as in Examples 3 and 4.
Or it turns out that the edge part of a gas barrier film can be made to curve suddenly like Example 5, 6, the width T of a diaphragm area can be made smaller, and a frame can be narrowed.
From the above results, the effects of the present invention are clear.

10 functional laminated film 12 functional layer 14 gas barrier film 20 gas barrier support 22 gas barrier layer 24 organic layer 26 inorganic layer

Claims

In a functional laminate film having a functional layer, and two gas barrier films having an inorganic layer, which are respectively laminated on one main surface and the other main surface of the functional layer,
The inorganic layer comprises silicon nitride,
The functional layer has at its end a squeeze area whose thickness is thinner than the average thickness of the functional layer,
The functional laminated film characterized in that the narrowed area is an area within a range of 10 mm or less from the end face of the functional layer, and the thickness at the end face is the thinnest.
The functional laminated film according to claim 1, wherein the squeeze area is an area in a range of 1 mm or less from the end face.
The functional laminated film according to claim 1, wherein a thickness of the functional layer at an end face is 50% or less of an average thickness of the functional layer.
The functional laminated film according to any one of claims 1 to 3, wherein the ends of the two gas barrier films are in contact with each other.
The functional laminated film according to any one of claims 1 to 4, wherein the thickness of the functional layer inside the narrowed region is ± 2% of the average thickness of the functional layer.
The functional laminated film according to any one of claims 1 to 5, wherein the uppermost layer on the functional layer side of the gas barrier film is the inorganic layer.
The gas barrier film according to any one of claims 1 to 6, comprising a gas barrier support, an organic layer laminated on the gas barrier support, and the inorganic layer laminated on the organic layer. Functional laminated film.
The functional laminated film according to any one of claims 1 to 7, wherein the thickness of the gas barrier film is 5 μm to 100 μm.
9. The functional laminate film according to claim 7, wherein the gas barrier support has a melting point of 230 ° C. or less and a glass transition temperature of 120 ° C. or less.
The water vapor transmission rate after extending the gas barrier film in the plane direction by 2.5% is 1 × 10 -3 [g / (m 2 · day)] or less according to any one of claims 1 to 9. Functional laminated film.
The functional laminated film according to any one of claims 1 to 10, wherein the inorganic layer has a hydrogen content of 10 atomic% to 30 atomic%.
The functional laminated film according to any one of claims 1 to 11, wherein the functional layer is a quantum dot layer including a large number of quantum dots.
Preparing a laminate having a functional layer, and two gas barrier films having an inorganic layer containing silicon nitride, which are respectively laminated on one principal surface and the other principal surface of the functional layer;
A cutting step of cutting the laminate to form a thickness of the functional layer within a range of 10 mm or less from the cut surface, thinner than the average thickness of the functional layer and the thinnest on the cut surface And a method of producing a functional laminate film.
The gas barrier film has a gas barrier support and the inorganic layer,
The method for producing a functional laminated film according to claim 13, wherein the cutting is performed by heating the blade temperature to a range of the glass transition temperature + 50 ° C to the melting point + 50 ° C of the gas barrier support.
The method for producing a functional laminated film according to claim 13, wherein the cutting step is performed using a Thomson blade, a cutting blade or a slitter blade.