JP2017074711A - Gas barrier film and production method of gas barrier film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier film having small absorption of light near a wavelength of 450 nm and excellent gas barrier property and adhesiveness between structural layers, and a production method of a gas barrier film.SOLUTION: A gas barrier film F has a base layer 2 and a gas barrier layer 3 formed in contact with the base layer on a resin substrate 1, in which the base layer 2 and the gas barrier layer 3 satisfy the following requirements. In the base layer 2, when an average composition of the layer is represented by SiOC(where v and w are stoichiometric factors), v and w satisfy 1.7≤v≤2.1 and 0.01≤w≤0.2; and the base layer has a thickness ranging from 50 to 200 nm. In the gas barrier layer 3, when an average composition of the layer is represented by SiOC(where x and y are stoichiometric factors), x and y satisfy 1.6≤x≤1.9, 0.15≤y≤0.40 and 4≤2x+2y<4.3; and the gas barrier layer has a thickness ranging from 15 to 50 nm.SELECTED DRAWING: Figure 1A

Description

  The present invention relates to a gas barrier film and a method for producing a gas barrier film. More specifically, the present invention relates to a gas barrier film having a small light absorption in the vicinity of a light wavelength of 450 nm and excellent in gas barrier properties and adhesion between constituent layers, and a method for producing the gas barrier film.

Conventionally, as a gas barrier layer used for a gas barrier film, a layer containing a compound having a SiO _{x Cy} composition by a chemical vapor deposition (CVD) method has been studied. In addition, for the adhesion between the base material and the gas barrier layer, a combination of the gas barrier layer with an anchor layer (corresponding to an underlayer in the present application) containing a compound in which a polyol and diisocyanate are urethane-bonded is studied. (For example, refer to Patent Document 1).

  In addition, when an organic component derived from polyorganosilsesquioxane is contained in an appropriate range ratio, a gas barrier layer by a CVD method having a good gas barrier property is obtained as an upper layer, and stored at high temperature and high humidity. In addition, an anchor layer excellent in heat resistance and excellent in heat resistance has also been studied (see, for example, Patent Document 2).

In recent studies, the gas barrier layer is a region having a relatively large amount of carbon component y of the SiO _x C _y composition (for example, the average composition is 0.1 ≦ y ≦ 1.0) and has a layer thickness of about 100 nm. It is known that a good gas barrier property can be obtained by forming a gas barrier layer by a CVD method. On the other hand, in a gas barrier layer containing a compound having the composition, light absorption in the vicinity of a light wavelength of 450 nm is achieved. There was a problem of being big.

  In particular, when the gas barrier layer is applied to a gas barrier film for a quantum dot sheet (hereinafter also referred to as a QD sheet), there is a problem that the luminance decrease estimated to be caused by light absorption near a light wavelength of 450 nm is large. It was.

However, in order to reduce the light absorption in the vicinity of the light wavelength of 450 nm, the light absorption and the gas in the vicinity of the light wavelength of 450 nm can be reduced only by adjusting the oxygen component x and the carbon component y of the compound having the SiO _x C _y composition by the CVD method. It is difficult to achieve both barrier properties and it is conceivable to improve the gas barrier properties in combination with an anchor layer, but there is a problem of a decrease in adhesion between the anchor layer and the gas barrier layer.

  Thus, in order to obtain good brightness as a gas barrier film for a QD sheet, a gas barrier film that has low light absorption near a light wavelength of 450 nm and excellent gas barrier properties and adhesion between constituent layers is required. ing.

JP 2011-178064 A JP 2006-123307 A

  The present invention has been made in view of the above-mentioned problems and situations, and the solution to the problem is a gas barrier film and a gas that have low gas absorption near a light wavelength of 450 nm and excellent gas barrier properties and adhesion between constituent layers. It is providing the manufacturing method of a barrier film.

  In order to solve the above-mentioned problems, the present inventor combined a compound having a specific composition, a base layer having a layer thickness, and a gas barrier layer on a resin base material in the process of examining the cause of the above-mentioned problem. The present inventors have found that a gas barrier film having a small light absorption near a light wavelength of 450 nm and excellent gas barrier properties and adhesion between constituent layers can be obtained.

  That is, the said subject which concerns on this invention is solved by the following means.

  1. A gas barrier film having a base layer and a gas barrier layer formed in contact with the base layer on a resin substrate, wherein the base layer and the gas barrier layer satisfy the following requirements: the film.

Underlayer: When the average composition is expressed by SiO _v C _w (where v and w are stoichiometric coefficients), 1.7 ≦ v ≦ 2.1, 0.01 ≦ w ≦ 0.2, and thickness Is in the range of 50 to 200 nm.

Gas barrier layer: When the average composition is expressed by SiO _x C _y (x and y are stoichiometric coefficients), 1.6 ≦ x ≦ 1.9, 0.15 ≦ y ≦ 0.40, and 4 ≦ 2x + 2y <4.3, and the thickness is in the range of 15 to 50 nm.

  2. The gas barrier film according to item 1, wherein the gas barrier layer further satisfies the following requirements.

  Gas barrier layer: product of y and thickness (nm) is in the range of 4-12.

  3. The said base layer contains metal M other than Si, and M / Si ratio (molar ratio) exists in the range of 0.001-0.05, The 1st term | claim or 2nd term | claim characterized by the above-mentioned. Gas barrier film.

  4). The gas barrier film according to any one of items 1 to 3, further comprising an adhesion layer containing an organosilicon compound having a polymerizable group on the gas barrier layer.

  5. The gas barrier film according to item 4, wherein the thickness of the adhesion layer is 5 nm or less.

  6). A method for producing a gas barrier film in which a coating layer containing polysilazane is formed as a base layer on a resin substrate, and a chemical vapor deposition layer is formed as a gas barrier layer in contact therewith, wherein the base layer and the gas barrier A method for producing a gas barrier film, wherein the layer satisfies the following requirements.

Underlayer: When the average composition is expressed by SiO _v C _w (where v and w are stoichiometric coefficients), 1.7 ≦ v ≦ 2.1, 0.01 ≦ w ≦ 0.2, and thickness Is in the range of 50 to 200 nm.

Gas barrier layer: When the average composition is expressed by SiO _x C _y (x and y are stoichiometric coefficients), 1.6 ≦ x ≦ 1.9, 0.15 ≦ y ≦ 0.40, and 4 ≦ 2x + 2y <4.3, and the thickness is in the range of 15 to 50 nm.

  7). The method for producing a gas barrier film according to claim 6, wherein the gas barrier layer further satisfies the following requirements.

  Gas barrier layer: product of y and thickness (nm) is in the range of 4-12.

  8). The gas barrier according to item 6 or 7, wherein the gas barrier layer further contains a metal M other than Si, and the M / Si ratio is in the range of 0.001 to 0.05. Sex film.

  9. The gas barrier film according to any one of claims 6 to 8, wherein an adhesion layer containing an organosilicon compound having a polymerizable group is further formed on the gas barrier layer. Production method.

  10. The method for producing a gas barrier film according to item 9, wherein a surface treatment step is added between the gas barrier layer and the adhesion layer.

  11. 11. The method for producing a gas barrier film according to claim 10, wherein the surface treatment step is performed with an apparatus used for forming the gas barrier layer after the gas barrier layer is formed.

  By the above means of the present invention, it is possible to provide a gas barrier film having a small light absorption in the vicinity of a light wavelength of 450 nm and excellent in gas barrier properties and adhesion between constituent layers, and a method for producing the gas barrier film.

  The expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.

  The characteristic of the gas barrier film of the present invention is that a compound having a specific composition, an underlayer having a layer thickness, and a gas barrier layer are combined on a resin substrate.

The underlayer is a layer whose average composition is represented by SiO _v C _w (for example, a layer obtained by modifying polysilazane), and v and w are 1.7 ≦ v ≦ 2.1, 0.01 ≦ It is in the range of w ≦ 0.2, and the layer thickness is in the range of 50 to 200 nm.

  The carbon component w is contained in the layer by adding an organic metal compound such as an organic Si compound or ALCH at the time of layer formation, but is required to be 0.01 or more from the viewpoint of film strength and flexibility, and is transparent. From the viewpoint of safety, it is necessary to be 0.2 or less.

  In addition, when the oxygen component v is less than 1.7, it indicates that N remains excessively, outgas of ammonia or hydrogen is generated when the gas barrier layer is formed by the CVD method, and the film quality of the gas barrier layer is There is a concern that the gas barrier properties deteriorate due to deterioration. In addition, when v exceeds 2.1, it indicates that Si—OH is excessively present, water vapor outgas is generated when the gas barrier layer is formed by the CVD method, and the film quality of the gas barrier layer is deteriorated. Gas barrier properties are reduced. Therefore, it is presumed that the influence on the gas barrier property of the upper gas barrier layer can be reduced by controlling within the above range.

  Furthermore, when the thickness of the underlayer is less than 50 nm, there is a concern that the gas barrier layer is defective due to the surface unevenness of the resin substrate, and the gas barrier property is greatly deteriorated. If the thickness exceeds 200 nm, the total amount of outgas causing substances contained in the underlayer increases, and even if v and w are within the above ranges, there is a concern that the gas barrier property may be deteriorated due to outgassing. Needs to be within the above range.

  In addition, regarding the adhesiveness, it is presumed that the use of the same kind of material that is a silicon oxide compound in the base layer and the gas barrier layer increases the affinity between the layers and improves the adhesiveness.

On the other hand, the gas barrier layer has 1.6 ≦ x ≦ 1.9, 0.15 ≦ y ≦ 0.40, and 4 ≦ 2x + 2y <4.3 when the average composition is expressed by SiO _x C _y. And the thickness is in the range of 15 to 50 nm. By setting it as this range, it is possible to balance improvement in gas barrier properties and reduction in light absorption in the vicinity of a light wavelength of 450 nm.

  The ranges of the values of the oxygen component x and the carbon component y are regions optimized from the viewpoint of gas barrier properties and transparency. When the oxygen component x increases, the transparency tends to improve, and when it decreases, the gas barrier property improves. Moreover, when the carbon component y increases, the transparency tends to deteriorate. Therefore, if it is in the range of the value of said x and y, it will be guessed that the balance of gas barrier property and transparency can be taken.

In addition, for example, in the formation of a gas barrier layer by a CVD method using hexamethyldisiloxane (HMDSO) as a raw material, the gas barrier layer mainly includes Si—O—Si bonds or Si—CH ₂ —Si bonds. It is thought to have. If all are Si—O—Si bonds or Si—CH ₂ —Si bonds, 2x + 2y = 4, but in reality, since a small amount of Si—CH ₃ exists, it is considered that 4 <2x + 2y. . Therefore, when 2x + 2y is 4.3 or more, it is considered that Si—CH ₃ is excessively present, and the gas barrier property is greatly lowered. When 2x + 2y is less than 4, a so-called oxygen deficiency state occurs, the light absorption at a light wavelength of 450 nm greatly increases, and the luminance deteriorates when applied to a QD sheet.

Accordingly, the gas barrier layer according to the present invention, the average composition of the compounds contained in the gas barrier layer when expressed in SiO _x C _y, a range of values of the x and y, and is defined by 2x + 2y It is presumed that by controlling the content of Si—CH ₃ , the gas barrier property can be improved and the light absorption in the vicinity of the light wavelength of 450 nm can be reduced.

  Particularly in the case of a gas barrier layer, when the product of y and thickness (nm) increases, the gas barrier property improves, and conversely, light absorption near a wavelength of 450 nm increases, and the y and thickness are increased. When the product with (nm) is small, the gas barrier property is deteriorated, the light absorption is in a direction to be small, and good when the product of y and thickness (nm) is in the range of 4 to 12. It is assumed that a good performance balance can be obtained.

Sectional drawing which shows the example of the gas barrier film of this invention Sectional drawing which shows the example of the QD sheet using the gas barrier film of this invention The schematic diagram which shows an example of the vacuum plasma CVD apparatus used for formation of the CVD layer which is a preferable form of the gas barrier layer concerning this invention Schematic diagram showing another example of a vacuum plasma CVD apparatus

  The gas barrier film of the present invention is a gas barrier film having a base layer and a gas barrier layer formed in contact with the base layer on the resin base material. The base layer and the gas barrier layer satisfy the following requirements. It is characterized by satisfying.

Underlayer: When the average composition is expressed by SiO _v C _w (where v and w are stoichiometric coefficients), 1.7 ≦ v ≦ 2.1, 0.01 ≦ w ≦ 0.2, and thickness Is in the range of 50 to 200 nm.

Gas barrier layer: When the average composition is expressed by SiO _x C _y (x and y are stoichiometric coefficients), 1.6 ≦ x ≦ 1.9, 0.15 ≦ y ≦ 0.40, and 4 ≦ 2x + 2y <4.3, and the thickness is in the range of 15 to 50 nm.

  This feature is a technical feature common to the inventions according to claims 1 to 11.

  As an embodiment of the present invention, it is preferable that the gas barrier layer further has a product of y and thickness (nm) in the range of 4 to 12 from the viewpoint of manifesting the effect of the present invention. From the viewpoint of balancing the properties and light absorption in the vicinity of a wavelength of 450 nm, it is preferable.

  The underlayer further contains a metal M other than Si, and the M / Si ratio is preferably in the range of 0.001 to 0.05. When a metal M other than Si is added, N contained at the time of coating and drying is replaced with O, and it is possible to efficiently make the composition of v and w within the above range even under conditions where the energy of the modification treatment is low. It becomes.

  In addition, when the gas barrier film of the present invention is applied to a QD sheet, the adhesive layer containing an organosilicon compound having a polymerizable group on the gas barrier layer further improves the adhesion. Therefore, it is preferable. The adhesion layer may be a thin film as long as it exhibits an effect, and the thickness is preferably 5 nm or less.

  The method for producing a gas barrier film of the present invention is a gas barrier film in which a coating layer containing polysilazane is formed as a base layer on a resin substrate, and a chemical vapor deposition layer is formed as a gas barrier layer in contact therewith. The manufacturing method is characterized in that the underlayer and the gas barrier layer satisfy the following requirements.

Underlayer: When the average composition is expressed by SiO _v C _w , 1.7 ≦ v ≦ 2.1, 0.01 ≦ w ≦ 0.2, and the thickness is in the range of 50 nm to 200 nm. .

Gas barrier layer: When representing the average composition in _SiO x _{C y,} a 1.6 ≦ x ≦ 1.9,0.15 ≦ y ≦ 0.40, and a 4 ≦ 2x + 2y <4.3, The thickness is in the range of 15-50 nm.

  In addition, the gas barrier layer further satisfies the requirement that the product of y and thickness (nm) is in the range of 4 to 12, from the viewpoint of obtaining a good performance balance between gas barrier properties and luminance. preferable.

  The underlayer further contains a metal M other than Si, and that the M / Si ratio (molar ratio) is within the range of 0.001 to 0.05, N contained during coating and drying is replaced with O, Even under conditions where the energy of the reforming treatment is low, it is possible to make the composition in which the v and w are within the above-mentioned range efficiently, which is preferable.

  From the viewpoint of adhesion with the QD-containing resin layer when the gas barrier film is applied to a QD sheet, forming an adhesion layer containing an organosilicon compound having a polymerizable group on the gas barrier layer. preferable.

  Furthermore, it is preferable to add a surface treatment step between the gas barrier layer and the adhesion layer from the viewpoint of further improving the adhesion.

  Moreover, it is a preferable aspect from a viewpoint of production efficiency that the said surface treatment process is performed with the apparatus used for formation of the said gas barrier layer after forming the said gas barrier layer.

  Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, in this application, "-" is used in the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit.

<< Outline of Gas Barrier Film of the Present Invention >>
The gas barrier film of the present invention is a gas barrier film having a base layer and a gas barrier layer formed in contact with the base layer on the resin base material. The base layer and the gas barrier layer satisfy the following requirements. It is characterized by satisfying.

Underlayer: When the average composition is expressed by SiO _v C _w (where v and w are stoichiometric coefficients), 1.7 ≦ v ≦ 2.1, 0.01 ≦ w ≦ 0.2, and thickness Is in the range of 50 to 200 nm.

Gas barrier layer: When the average composition is expressed by SiO _x C _y (x and y are stoichiometric coefficients), 1.6 ≦ x ≦ 1.9, 0.15 ≦ y ≦ 0.40, and 4 ≦ 2x + 2y <4.3, and the thickness is in the range of 15 to 50 nm.

The “gas barrier property” as used in the present invention is a water vapor permeability (temperature: 60 ± 0.5 ° C., relative humidity (RH): 90 ± 2%) measured by a method according to JIS K 7129-1992. 1 × 10 ⁻² g / m ² · 24 h or less, and the oxygen permeability measured by a method according to JIS K 7126-1987 is 1 × 10 ⁻² ml / m ² · 24 h · atm or less. means.

In addition, the expression “SiO _v C _w ” or “SiO _x C _y ” represents the average composition of the base layer and the gas barrier layer refers to the compound constituting the layer or the average composition of the compound.

<Composition analysis by XPS>
The compositions v and _w in the SiO _v C _w contained in the underlayer according to the present invention and the compositions x and y in the SiO _x C _y contained in the gas barrier layer according to the present invention are expressed by X-ray photoelectron spectroscopy ( It can be obtained by measuring and averaging the element concentration distribution in the layer thickness direction by XPS (Xray Photoelectron Spectroscopy).

  The XPS analysis in the present invention is performed under the following conditions, but even if the apparatus and measurement conditions are changed, any measurement method that conforms to the gist of the present invention can be applied without any problem.

  The measurement method according to the gist of the present invention is mainly the resolution in the layer thickness direction, and the etching depth per measurement point (corresponding to the conditions of the following sputter ion and depth profile) is 3 nm or less. Is preferably 2 nm or less, and more preferably 1 nm or less.

  An example of specific conditions for XPS analysis applicable to the present invention is shown below.

・ Analyzer: QUANTERASXM manufactured by ULVAC-PHI
・ X-ray source: Monochromatic Al-Kα
・ Sputtering ion: Ar (2 keV)
Depth profile: Measurement is repeated at a predetermined thickness interval with a SiO ₂ equivalent sputtering thickness to obtain a depth profile in the depth direction. The thickness interval was 1 nm (data every 1 nm is obtained in the depth direction).

  Quantification: The background was determined by the Shirley method, and quantified using the relative sensitivity coefficient method from the obtained peak area. Data processing uses MultiPak manufactured by ULVAC-PHI.

  FIG. 1 is a cross-sectional view showing a structural example of a gas barrier film of the present invention.

  FIG. 1A shows a minimum configuration of a gas barrier film F of the present invention in which a base layer 2 is formed on a resin substrate 1 and a gas barrier layer 3 is laminated thereon.

  FIG. 1B is a cross-sectional view showing a QD sheet G in which an adhesion layer 4 is further formed on the gas barrier layer 3 and a QD-containing resin layer 5 is laminated thereon.

  Although other functional layers are not shown in FIG. 1, an antistatic layer, a backcoat layer, a bleedout prevention layer, a hard coat layer, and the like may be appropriately laminated. Furthermore, the structure which formed the base layer 2 and the gas barrier layer 3 on the both sides of the resin base material 1 may be sufficient.

[1] Resin As the resin substrate used in the gas barrier film of the present invention, a plastic film is preferably used. The plastic film to be used is not particularly limited in material, thickness, and the like as long as it can hold an underlayer, a gas barrier layer, and the like, and can be appropriately selected according to the purpose of use. Specific examples of the plastic film include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, polyamideimide resin, and polyetherimide. Resin, cellulose acylate resin, polyurethane resin, polyetheretherketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyethersulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring-modified polycarbonate resin, alicyclic ring Examples thereof include thermoplastic resins such as modified polycarbonate resins, fluorene ring-modified polyester resins, and acryloyl compounds.

  The thickness of the resin base material is preferably about 5 to 500 μm, more preferably 15 to 250 μm.

  In addition, as for the type of the base material and the manufacturing method of the base material, the techniques disclosed in paragraphs “0125” to “0136” of JP2013-226758A can be appropriately employed.

[2] Underlayer The underlayer is a layer containing a silicon oxide compound. When the average composition is expressed by SiO _v C _w , 1.7 ≦ v ≦ 2.1, 0.01 ≦ w ≦ 0. 2 and the thickness is in the range of 50 to 200 nm.

  The w needs to be 0.01 or more from the viewpoint of film strength and flexibility, and w or less from the viewpoint of transparency.

  Further, when v is less than 1.7, it indicates that N remains excessively, and ammonia or hydrogen outgas is generated when the gas barrier layer is formed by the CVD method, and the film quality of the gas barrier layer is deteriorated. There is a concern that the gas barrier property is lowered. In addition, when v exceeds 2.1, it indicates that Si—OH is excessively present, water vapor outgas is generated when the gas barrier layer is formed by the CVD method, and the film quality of the gas barrier layer is deteriorated. Gas barrier properties are reduced. Therefore, in order to reduce the influence on the gas barrier property of the upper gas barrier layer, it is necessary to control within the above range.

  Furthermore, if the thickness of the underlayer is less than 50 nm, there is a concern that the gas barrier property is greatly deteriorated due to the surface unevenness of the resin base material, and if it exceeds 200 nm, the total amount of the cause of outgas contained in the underlayer is Therefore, even if v and w are within the above range, there is a concern that the gas barrier property is deteriorated due to outgassing, and thus the layer thickness needs to be within the above range.

  The underlayer according to the present invention is formed by applying energy to a coating film formed by applying a coating liquid containing polysilazane because there are few defects such as film formability and cracks (coating film formation). It is preferable that it is formed by the method.

  In the composition, carbon C is contained in the coating layer by adding an organic metal compound such as an organic Si compound or ALCH to the coating solution. It can be controlled by the amount added (initial value at the time of coating formation) and the processing energy after coating (heat treatment, UV processing, VUV (excimer) processing). is there.

  The base layer may be a single layer or a laminated structure of two or more layers. Further, when the underlayer has a laminated structure of two or more layers, each underlayer may have the same composition or a different composition.

  Examples of the polysilazane include perhydropolysilazane, organopolysilazane, and the like, but perhydropolysilazane is preferable because there are few residual organic substances.

Polysilazane is a polymer having a silicon-nitrogen bond, and ceramics such as SiO ₂ , Si ₃ N ₄ , and both intermediate solid solutions SiO _x N _y having bonds such as Si—N, Si—H, and N—H. It is a precursor inorganic polymer.

  Specifically, the polysilazane preferably has the following structure.

上記一般式（Ｉ）において、Ｒ_１、Ｒ_２及びＲ_３は、それぞれ独立して、水素原子、置換又は非置換の、アルキル基、アリール基、ビニル基又は（トリアルコキシシリル）アルキル基である。この際、Ｒ_１、Ｒ_２及びＲ_３は、それぞれ、同じであっても又は異なってもよい。ここで、アルキル基としては、炭素原子数１〜８の直鎖、分岐鎖又は環状のアルキル基が挙げられる。より具体的には、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、イソペンチル基、ネオペンチル基、ｎ−ヘキシル基、ｎ−ヘプチル基、ｎ−オクチル基、２−エチルヘキシル基、シクロプロピル基、シクロペンチル基、シクロヘキシル基などがある。また、アリール基としては、炭素原子数６〜３０のアリール基が挙げられる。より具体的には、フェニル基、ビフェニル基、ターフェニル基などの非縮合炭化水素基；ペンタレニル基、インデニル基、ナフチル基、アズレニル基、ヘプタレニル基、ビフェニレニル基、フルオレニル基、アセナフチレニル基、プレイアデニル基、アセナフテニル基、フェナレニル基、フェナントリル基、アントリル基、フルオランテニル基、アセフェナントリレニル基、アセアントリレニル基、トリフェニレニル基、ピレニル基、クリセニル基、ナフタセニル基などの縮合多環炭化水素基が挙げられる。（トリアルコキシシリル）アルキル基としては、炭素原子数１〜８のアルコキシ基で置換されたシリル基を有する炭素原子数１〜８のアルキル基が挙げられる。より具体的には、３−（トリエトキシシリル）プロピル基、３−（トリメトキシシリル）プロピル基などが挙げられる。上記Ｒ_１〜Ｒ_３に場合によって存在する置換基は、特に制限はないが、例えば、アルキル基、ハロゲン原子、ヒドロキシ基（−ＯＨ）、メルカプト基（−ＳＨ）、シアノ基（−ＣＮ）、スルホ基（−ＳＯ_３Ｈ）、カルボキシ基（−ＣＯＯＨ）、ニトロ基（−ＮＯ_２）などがある。なお、場合によって存在する置換基は、置換するＲ_１〜Ｒ_３と同じとなることはない。例えば、Ｒ_１〜Ｒ_３がアルキル基の場合には、さらにアルキル基で置換されることはない。これらのうち、好ましくは、Ｒ_１、Ｒ_２及びＲ_３は、水素原子、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、フェニル基、ビニル基、３−（トリエトキシシリル）プロピル基又は３−（トリメトキシシリルプロピル）基である。

In the general formula (I), R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group. . In this case, R ₁ , R ₂ and R ₃ may be the same or different. Here, as an alkyl group, a C1-C8 linear, branched or cyclic alkyl group is mentioned. More specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n -Hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like. Moreover, as an aryl group, a C6-C30 aryl group is mentioned. More specifically, non-condensed hydrocarbon groups such as phenyl group, biphenyl group, terphenyl group; pentarenyl group, indenyl group, naphthyl group, azulenyl group, heptaenyl group, biphenylenyl group, fluorenyl group, acenaphthylenyl group, preadenenyl group , Condensed polycyclic hydrocarbon groups such as acenaphthenyl group, phenalenyl group, phenanthryl group, anthryl group, fluoranthenyl group, acephenanthrenyl group, aceantrirenyl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, etc. Can be mentioned. Examples of the (trialkoxysilyl) alkyl group include an alkyl group having 1 to 8 carbon atoms having a silyl group substituted with an alkoxy group having 1 to 8 carbon atoms. More specifically, 3- (triethoxysilyl) propyl group, 3- (trimethoxysilyl) propyl group and the like can be mentioned. The substituent optionally present in R _{1 to} R ₃ is not particularly limited. For example, an alkyl group, a halogen atom, a hydroxy group (—OH), a mercapto group (—SH), a cyano group (—CN), There are a sulfo group (—SO ₃ H), a carboxy group (—COOH), a nitro group (—NO ₂ ), and the like. In addition, the substituent which exists depending on the case does not become the same as R < ₁ > -R < ₃ > to substitute. For example, when R _{1 to} R ₃ are alkyl groups, they are not further substituted with an alkyl group. Of these, R ₁ , R ₂ and R ₃ are preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a phenyl group, a vinyl group, 3 -(Triethoxysilyl) propyl group or 3- (trimethoxysilylpropyl) group.

  Moreover, in the said general formula (I), n is an integer, and it is preferable to determine so that the polysilazane which has a structure represented by general formula (I) may have a number average molecular weight of 150-150,000 g / mol.

In the compound having the structure represented by the general formula (I), one of preferred embodiments is perhydropolysilazane in which all of R ₁ , R ₂ and R ₃ are hydrogen atoms. The underlayer formed from such polysilazane has high density.

  Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on 6- and 8-membered rings. The molecular weight is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn), and there are liquid or solid substances, and the state varies depending on the molecular weight.

  Polysilazane is commercially available in the form of a solution dissolved in an organic solvent, and a commercially available product may be used as it is as a coating solution for forming an underlayer, or a plurality of commercially available products may be mixed and used. Moreover, you may dilute and use a commercial item with a suitable solvent. As a commercially available product of polysilazane solution, NN120-10, NN120-20, NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL120-20, NL150A, NP110, NP140, SP140, etc. manufactured by AZ Electronic Materials Co., Ltd. Is mentioned.

  In addition, for details of polysilazane, paragraphs “0024” to “0040” of JP2013-255910A, paragraphs “0037” to “0043” of JP2013-188942A, and JP2013-103A are known. No. 151123, paragraphs “0014” to “0021”, JP 2013-052569 A paragraphs “0033” to “0045”, JP 2013-129557 A paragraphs “0062” to “0075”, JP 2013 It can be adopted with reference to paragraphs “0037” to “0064” of JP-A-226758.

  When polysilazane is used, the content of polysilazane in the underlayer before energy application can be 100% by mass when the total mass of the underlayer is 100% by mass. In addition, when the underlayer contains a material other than polysilazane, the content of polysilazane in the underlayer is preferably in the range of 10 to 99% by mass, and in the range of 40 to 95% by mass. Is more preferable, and particularly preferably in the range of 70 to 95% by mass.

<Other metals>
The underlayer according to the present invention further contains a metal M other than Si, and the M / Si ratio (molar ratio) is preferably in the range of 0.001 to 0.05.

  When an organometallic compound of Al, B, Ti, or Zr is added to the coating solution as a metal M other than Si, N contained in the polysilazane is replaced with O during coating and drying, and the energy of the modification treatment after coating is low Also, the composition can efficiently make v and w fall within the above range.

  Examples of metal elements include aluminum (Al), titanium (Ti), zirconium (Zr), zinc (Zn), gallium (Ga), indium (In), chromium (Cr), iron (Fe), magnesium (Mg ), Tin (Sn), nickel (Ni), palladium (Pd), lead (Pb), manganese (Mn), lithium (Li), germanium (Ge), copper (Cu), sodium (Na), potassium (K ), Calcium (Ca), cobalt (Co), boron (B), beryllium (Be), strontium (Sr), barium (Ba), radium (Ra), thallium (Tl), germanium (Ge) and the like. .

  In particular, Al, B, Ti and Zr are preferable, and among them, an organometallic compound containing Al is preferable.

  Examples of the aluminum compound applicable to the present invention include aluminum isopoloxide, aluminum-sec-butyrate, titanium isopropoxide, aluminum triethylate, aluminum triisopropylate, aluminum tritert-butylate, aluminum tri-n- Examples include butyrate, aluminum trisec-butyrate, aluminum ethyl acetoacetate / diisopropylate, acetoalkoxyaluminum diisopropylate, aluminum diisopropylate monoaluminum-t-butylate, aluminum trisethylacetoacetate, aluminum oxide isopropoxide trimer, etc. be able to.

  Specific commercial products include, for example, AMD (aluminum diisopropylate monosec-butyrate), ASBD (aluminum secondary butyrate), ALCH (aluminum ethyl acetoacetate / diisopropylate), ALCH-TR (aluminum trisethylacetate). Acetate), aluminum chelate M (aluminum alkyl acetoacetate / diisopropylate), aluminum chelate D (aluminum bisethylacetoacetate / monoacetylacetonate), aluminum chelate A (W) (aluminum trisacetylacetonate) Ken Fine Chemical Co., Ltd.), Preneact (registered trademark) AL-M (acetoalkoxy aluminum diisopropylate, Ajinomoto Fine Chemical Co., Ltd.), etc. It is possible.

  In addition, when using these compounds, it is preferable to mix with the coating liquid containing polysilazane in inert gas atmosphere. This is to prevent these compounds from reacting with moisture and oxygen in the atmosphere and causing intense oxidation. Moreover, when mixing these compounds and polysilazane, it is preferable to heat up to 30-100 degreeC, and to hold | maintain for 1 minute-24 hours, stirring.

<Underlayer forming coating solution>
The solvent for preparing the coating solution for forming the underlayer is not particularly limited as long as it can dissolve polysilazane, but water and reactive groups that easily react with polysilazane (for example, hydroxy groups or amine groups). Etc.), an organic solvent inert to polysilazane is preferred, and an aprotic organic solvent is more preferred. Specifically, the solvent is an aprotic solvent; for example, carbon such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso, terpenes, etc. Hydrogen solvents; Halogen hydrocarbon solvents such as methylene chloride and trichloroethane; Esters such as ethyl acetate and butyl acetate; Ketones such as acetone and methyl ethyl ketone; Aliphatic ethers such as dibutyl ether, dioxane and tetrahydrofuran; Alicyclic ethers and the like Ethers: Examples include tetrahydrofuran, dibutyl ether, mono- and polyalkylene glycol dialkyl ethers (diglymes), and the like. The solvent is selected according to purposes such as the solubility of the silicon compound and the evaporation rate of the solvent, and may be used alone or in the form of a mixture of two or more.

  The concentration of polysilazane in the coating solution for forming the underlayer is not particularly limited, and varies depending on the thickness of the underlayer and the pot life of the coating solution, but preferably 1 to 80% by mass, more preferably 5 to 50% by mass, More preferably, it is 10-40 mass%.

  The underlayer-forming coating solution preferably contains a catalyst in order to promote reforming. As the catalyst applicable to the present invention, a basic catalyst is preferable, and in particular, N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, Amine catalysts such as N ', N'-tetramethyl-1,3-diaminopropane, N, N, N', N'-tetramethyl-1,6-diaminohexane, Pt compounds such as Pt acetylacetonate, propion Examples thereof include metal catalysts such as Pd compounds such as acid Pd, Rh compounds such as Rh acetylacetonate, and N-heterocyclic compounds. Of these, it is preferable to use an amine catalyst. The concentration of the catalyst added at this time is preferably in the range of 0.1 to 10% by mass, more preferably 0.5 to 7% by mass, based on the silicon compound. By setting the amount of the catalyst to be in this range, it is possible to avoid excessive silanol formation due to rapid progress of the reaction, decrease in film density, increase in film defects, and the like.

  Additives listed below can be used in the coating solution for forming the underlayer, if necessary. For example, cellulose ethers, cellulose esters; for example, ethyl cellulose, nitrocellulose, cellulose acetate, cellulose acetobutyrate, etc., natural resins; for example, rubber, rosin resin, etc., synthetic resins; Aminoplasts, especially urea resins, melamine formaldehyde resins, alkyd resins, acrylic resins, polyesters or modified polyesters, epoxides, polyisocyanates or blocked polyisocyanates, polysiloxanes, and the like.

<Method of forming a layer containing polysilazane>
The layer containing polysilazane can be formed by applying the above base layer-forming coating solution on a substrate. As a coating method, a conventionally known appropriate wet coating method can be adopted. Specific examples include spin coating method, roll coating method, flow coating method, ink jet method, spray coating method, printing method, dip coating method, casting film forming method, bar coating method, die coating method, gravure printing method and the like. It is done.

  The coating thickness can be appropriately selected according to the thickness of the underlayer.

  After applying the coating solution, it is preferable to dry the coating film. By drying the coating film, the organic solvent contained in the coating film can be removed. At this time, all of the organic solvent contained in the coating film may be dried or may be partially left. Even when a part of the organic solvent is left, a suitable underlayer can be obtained. The remaining solvent can be removed later.

  Although the drying temperature of a coating film changes also with the base material to apply, it is preferable that it is 50-200 degreeC. For example, when a polyethylene terephthalate substrate having a glass transition temperature (Tg) of 70 ° C. is used as the substrate, the drying temperature is preferably set to 150 ° C. or less in consideration of deformation of the substrate due to heat.

<Applying energy>
Subsequently, energy is applied to the polysilazane-containing layer formed as described above to modify the polysilazane and modify the underlying layer.

  As a method for applying energy to the polysilazane-containing layer, a known method can be appropriately selected and applied. Specific examples of the modification treatment include plasma treatment, ultraviolet irradiation treatment, and heat treatment. However, in the case of modification by heat treatment, since a high temperature of 450 ° C. or higher is required, adaptation is difficult for flexible substrates such as plastic. For this reason, it is preferable to perform the heat treatment in combination with other reforming treatments.

  Therefore, as the modification treatment, from the viewpoint of adapting to a plastic substrate, a plasma treatment capable of a conversion reaction at a lower temperature or a conversion reaction by ultraviolet irradiation treatment is preferable.

  Hereinafter, plasma treatment and ultraviolet irradiation treatment, which are preferable modification treatment methods, will be described.

(Plasma treatment)
In the present invention, a known method can be used as the plasma treatment that can be used as the modification treatment, and an atmospheric pressure plasma treatment or the like can be preferably used. The atmospheric pressure plasma CVD method, which performs plasma CVD processing near atmospheric pressure, does not need to be reduced in pressure and is more productive than the plasma CVD method under vacuum. The film speed is high, and further, under a high pressure condition under atmospheric pressure as compared with the conditions of a normal CVD method, the gas mean free process is very short, so that a very homogeneous film can be obtained.

  In the case of atmospheric pressure plasma treatment, as the discharge gas, nitrogen gas or a gas containing Group 18 atoms in the long-period periodic table, specifically helium, neon, argon, krypton, xenon, radon, or the like is used. Among these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.

(UV irradiation treatment)
As one of the modification treatment methods, treatment by ultraviolet irradiation is preferable. Ozone and active oxygen atoms generated by ultraviolet rays (synonymous with ultraviolet light) have high oxidation ability, and can form silicon oxide films or silicon oxynitride films with high density and insulation at low temperatures. It is.

This UV irradiation heats the base material and excites and activates O ₂ and H ₂ O that contribute to ceramics conversion (silica conversion), UV absorbers, and polysilazanes themselves, thus promoting the conversion of polysilazanes into ceramics. Moreover, the obtained underlayer becomes denser. Irradiation with ultraviolet rays is effective at any time after the formation of the coating film.

  In the ultraviolet irradiation treatment, any commonly used ultraviolet ray generator can be used.

  The ultraviolet ray referred to in the present invention generally refers to an electromagnetic wave having a wavelength of 10 to 400 nm, but in the case of an ultraviolet irradiation treatment other than the vacuum ultraviolet ray (10 to 200 nm) treatment described later, it is preferably 210 to 375 nm. Use ultraviolet light.

  For the irradiation with ultraviolet rays, it is preferable to set the irradiation intensity and the irradiation time as long as the substrate carrying the irradiated underlayer is not damaged.

For example, when a plastic film is used as the substrate, for example, a 2 kW (80 W / cm × 25 cm) lamp is used, and the strength of the substrate surface is 20 to 300 mW / cm ² , preferably 50 to 200 mW / cm. The distance between the substrate and the ultraviolet irradiation lamp is set so as to be ^2, and irradiation can be performed for 0.1 second to 10 minutes.

  In general, when the substrate temperature during ultraviolet irradiation treatment is 150 ° C. or more, in the case of a plastic film or the like, the properties of the substrate are impaired, such as deformation of the substrate or deterioration of its strength. Become. However, in the case of a film having high heat resistance such as polyimide, a modification treatment at a higher temperature is possible. Accordingly, there is no general upper limit for the substrate temperature at the time of ultraviolet irradiation, and it can be appropriately set by those skilled in the art depending on the type of substrate. Moreover, there is no restriction | limiting in particular in ultraviolet irradiation atmosphere, What is necessary is just to implement in air.

  Examples of such ultraviolet ray generating means include metal halide lamps, high pressure mercury lamps, low pressure mercury lamps, xenon arc lamps, carbon arc lamps, and excimer lamps (single wavelengths of 172 nm, 222 nm, and 308 nm, for example, USHIO INC. Manufactured by M.D. Com Co., Ltd.), UV light laser, and the like, but are not particularly limited. In addition, when irradiating the layer containing polysilazane with the generated ultraviolet ray, from the viewpoint of achieving efficiency improvement and uniform irradiation, the layer containing polysilazane is reflected after reflecting the ultraviolet ray from the generation source with a reflector. It is preferable to apply.

  The ultraviolet irradiation can be adapted to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate to be used. For example, in the case of batch processing, a laminate having a polysilazane-containing layer on its surface can be processed in an ultraviolet baking furnace equipped with an ultraviolet source as described above. The ultraviolet baking furnace itself is generally known. For example, an ultraviolet baking furnace manufactured by I-Graphics Co., Ltd. can be used. Moreover, when the laminated body which has the layer containing polysilazane on the surface is a long film form, it irradiates with an ultraviolet-ray continuously in the drying zone equipped with the above ultraviolet ray generation sources, conveying this. Can be made into ceramics. The time required for ultraviolet irradiation is generally 0.1 seconds to 10 minutes, preferably 0.5 seconds to 3 minutes, although it depends on the composition and concentration of the base material used and the layer containing polysilazane.

(Vacuum ultraviolet irradiation treatment: excimer irradiation treatment)
In the present invention, the most preferable modification treatment method for the underlayer is a treatment by vacuum ultraviolet irradiation (excimer irradiation treatment). The treatment by vacuum ultraviolet irradiation uses light energy of 100 to 200 nm, preferably light energy with a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the polysilazane compound, and bonds the atoms with only photons called photon processes. This is a method of forming a silicon oxide film at a relatively low temperature (about 200 ° C. or lower) by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly by action.

  The radiation source in the present invention may be any radiation source that generates light having a wavelength of 100 to 180 nm, but preferably an excimer radiator (for example, a Xe excimer lamp) having a maximum emission at about 172 nm, and an emission line at about 185 nm. Low pressure mercury vapor lamps, medium and high pressure mercury vapor lamps having a wavelength component of 230 nm or less, and excimer lamps having maximum emission at about 222 nm.

  Oxygen is necessary for the reaction at the time of ultraviolet irradiation, but since vacuum ultraviolet rays are absorbed by oxygen, the efficiency in the ultraviolet irradiation process is likely to decrease. It is preferable to perform in a state where the water vapor concentration is low. That is, the oxygen concentration at the time of vacuum ultraviolet irradiation is preferably 10 to 20,000 volume ppm (0.001 to 2 volume%), and preferably 50 to 10,000 volume ppm (0.005 to 1 volume%). More preferably. Also, the water vapor concentration during the conversion process is preferably in the range of 1000 to 4000 ppm by volume.

  As a gas that satisfies the irradiation atmosphere used at the time of irradiation with vacuum ultraviolet rays, a dry inert gas is preferable, and a dry nitrogen gas is particularly preferable from the viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.

In vacuum ultraviolet irradiation step, preferably the intensity of the vacuum ultraviolet rays in the coating film surface for receiving a layer containing polysilazane is ^{1mW / cm 2 ~10W / cm 2} , more preferably 30~200mW / cm ² 50 to 160 mW / cm ² is more preferable. If it is less than 1 mW / cm ^2, there is a concern that the reforming efficiency is greatly reduced. If it exceeds 10 W / cm ² , there is a concern that the coating film may be ablated or the substrate may be damaged.

Irradiation energy amount of the VUV in the coated surface (irradiation amount) is preferably from ^{10mJ / cm 2 ~3J / cm 2} , more preferably ^{50mJ / cm 2 ~1J / cm 2} . If it is 10 mJ / cm ² or more, it is possible to avoid insufficient modification, and if it is 3 J / cm ² or less, generation of cracks due to excessive modification and thermal deformation of the substrate can be prevented.

Further, the vacuum ultraviolet light used, CO, may be generated by plasma formed in a gas comprising at least one CO ₂ and CH _4. Further, as the gas containing at least one of CO, CO ₂ and CH ₄ (hereinafter also referred to as carbon-containing gas), a carbon-containing gas may be used alone, but a rare gas or H ₂ is used as a main gas. It is preferable to add a small amount of carbon-containing gas. Examples of plasma generation methods include capacitively coupled plasma.

[3] Gas Barrier Layer The gas barrier film of the present invention has a gas barrier layer formed by a vacuum film formation method in contact with the base layer above the base layer.

Gas barrier layer according to the present invention contains a silicon oxide compound, when representing the average composition in _SiO x _{C y,} a 1.6 ≦ x ≦ 1.9,0.15 ≦ y ≦ 0.40, 4 ≦ 2x + 2y <4.3, and the thickness is in the range of 15 nm to 50 nm.

  The gas barrier layer preferably further has a product of y and thickness (nm) in the range of 4-12.

  As described above, the range of the values of the oxygen component x and the carbon component y is a region optimized from the viewpoint of gas barrier properties and transparency, and when the oxygen component x increases, the transparency tends to improve. Yes, gas barrier properties improve as the size is reduced. Moreover, when the carbon component y increases, the transparency tends to deteriorate. Therefore, if it is in the range of the value of said x and y, gas barrier property and transparency can be balanced.

Further, in the formation of a gas barrier layer by a CVD method using hexamethyldisiloxane (HMDSO) as a raw material, it is considered that the gas barrier layer mainly has Si—O—Si bonds or Si—CH ₂ —Si bonds. It is done. If all are Si—O—Si bonds or Si—CH ₂ —Si bonds, 2x + 2y = 4, but in reality, since a small amount of Si—CH ₃ exists, it is considered that 4 <2x + 2y. . Therefore, when 2x + 2y is 4.3 or more, it is considered that Si—CH ₃ is excessively present, and the gas barrier property is greatly lowered. When 2x + 2y is less than 4, a so-called oxygen deficiency state occurs, the light absorption at a light wavelength of 450 nm greatly increases, and the luminance deteriorates when applied to a QD sheet.

Therefore, the gas barrier layer according to the present invention has an improved gas barrier property and light resistance by controlling the content of Si—CH ₃ within the range of the values of x and y and defined by 2x + 2y. Light absorption in the vicinity of a wavelength of 450 nm can be reduced.

  Furthermore, when the product of the carbon component y and the thickness (nm) is increased, the gas barrier property is improved, and conversely, the light absorption near the wavelength of 450 nm is increased, and the carbon component y and the thickness (nm) are increased. ), The gas barrier properties are deteriorated, and the light absorption is reduced. Good performance is obtained when the product of y and thickness (nm) is in the range of 4 to 12. Balance is obtained.

  As a vacuum film formation method which is a preferable method for forming the gas barrier layer, there are a physical vapor deposition method (PVD method) and a chemical vapor deposition method (CVD method).

<Gas deposition method>
The physical vapor deposition method (PVD method) is a method of depositing a target material, for example, a thin film such as a carbon film, on the surface of the material in a gas phase by a physical method. For example, a sputtering method (DC Sputtering method, RF sputtering method, ion beam sputtering method, magnetron sputtering method, etc.), vacuum deposition method, ion plating method and the like.

  The chemical vapor deposition method (CVD method) is a method in which a raw material gas containing a target thin film component is supplied onto a substrate, and the film is deposited by a chemical reaction on the surface of the substrate or in the gas phase. In addition, for the purpose of activating the chemical reaction, there are methods for generating plasma and the like, and well-known CVD methods such as a thermal CVD method, catalytic chemical vapor deposition method, photo CVD method, vacuum plasma CVD method and the like can be mentioned. Although not particularly limited, it is preferable to apply a vacuum plasma CVD method from the viewpoints of film formation speed, processing area, flexibility of the obtained gas barrier layer, and gas barrier properties.

  For example, if a silicon compound is used as a raw material compound and oxygen is used as the decomposition gas, silicon oxide is generated. This is because highly active charged particles and active radicals exist in the plasma space at a high density, so that multistage chemical reactions are accelerated at high speed in the plasma space, and the elements present in the plasma space are thermodynamic. This is because it is converted into an extremely stable compound in a very short time.

In order to control the oxygen component x and the carbon component _y in the average composition SiO _x C _y , it is preferable to use a vacuum plasma CVD method. This can be achieved by controlling.

  For example, it can be controlled by appropriately combining the supply amount and ratio of the film forming raw material and oxygen, the transport speed during film formation, the number of film formations, and the like.

  In the following, a case where a gas barrier layer is manufactured using a facing roller type roll-to-roll film forming apparatus which forms a thin film by a vacuum plasma CVD method, which is a preferable film forming apparatus, will be exemplified. I will explain.

  FIG. 2 is a schematic view showing an example of a vacuum plasma CVD apparatus used for forming a CVD layer which is a preferred form of the gas barrier layer according to the present invention.

  As shown in FIG. 2, the film forming apparatus 100 includes a delivery roller 10, transport rollers 11 to 14, first and second film forming rollers 15 and 16, a take-up roller 17, a gas supply pipe 18, and plasma. The power supply 19 for generation | occurrence | production, the magnetic field generators 20 and 21, the vacuum chamber 30, the vacuum pump 40, and the control part 41 are provided.

  The delivery roller 10, the transport rollers 11 to 14, the first and second film forming rollers 15 and 16, and the take-up roller 17 are accommodated in the vacuum chamber 30.

  The delivery roller 10 feeds the base material 1 a installed in a state of being wound in advance toward the transport roller 11. The delivery roller 10 is a cylindrical roller extending in a direction perpendicular to the paper surface, and is wound around the delivery roller 10 by rotating counterclockwise by a drive motor (not shown) (see the arrow in FIG. 2). The base material 1a is sent out toward the transport roller 11.

  The transport rollers 11 to 14 are cylindrical rollers configured to be rotatable around a rotation axis substantially parallel to the delivery roller 10. The transport roller 11 is a roller for transporting the base material 1 a from the feed roller 10 to the film forming roller 15 while applying an appropriate tension to the base material 1 a. The transport rollers 12 and 13 are rollers for transporting the substrate 1 b from the film formation roller 15 to the film formation roller 16 while applying an appropriate tension to the substrate 1 b formed by the film formation roller 15. Further, the transport roller 14 is a roller for transporting the base material 1 b from the film formation roller 16 to the take-up roller 17 while applying an appropriate tension to the base material 1 b formed by the film formation roller 16.

  The first film forming roller 15 and the second film forming roller 16 are a pair of film forming rollers having a rotation axis substantially parallel to the delivery roller 10 and facing each other with a predetermined distance therebetween. The film forming roller 15 forms the base material 1 a and conveys the base material 1 b to the film forming roller 16 while applying an appropriate tension to the formed base material 1 b. The film formation roller 16 forms the base material 1b, and conveys the base material 1c to the conveyance roller 14 while applying an appropriate tension to the film-formed base material 1c.

  In the example shown in FIG. 2, the separation distance between the first film forming roller 15 and the second film forming roller 16 is a distance connecting the point A and the point B. The first and second film forming rollers 15 and 16 are discharge electrodes formed of a conductive material, and the first film forming roller 15 and the second film forming roller 16 are insulated from each other. In addition, the material and structure of the first and second film forming rollers 15 and 16 can be appropriately selected so as to achieve a desired function as an electrode.

  Further, the first film forming roller 15 and the second film forming roller 16 may be independently temperature controlled. Although the temperature of the 1st film-forming roller 15 and the 2nd film-forming roller 16 is not specifically limited, For example, although it is -30-100 degreeC, it exceeds the glass transition temperature of the base material 1a, and becomes too high temperature. If set, the substrate may be deformed by heat.

  Magnetic field generators 20 and 21 are installed in the first and second film forming rollers 15 and 16, respectively. A high frequency voltage for plasma generation is applied to the first film formation roller 15 and the second film formation roller 16 by a plasma generation power source 19. As a result, an electric field is formed in the film forming section S between the first film forming roller 15 and the second film forming roller 16, and discharge plasma of the film forming gas supplied from the gas supply pipe 18 is generated. The power source frequency of the plasma generating power source 19 can be arbitrarily set, but the apparatus of this configuration is, for example, 60 to 100 kHz, and the applied power is, for example, 1 to 10 kW with respect to the effective film forming width 1 m. .

  The take-up roller 17 has a rotation axis substantially parallel to the feed roller 10 and takes up the base material 1c and stores it in the form of a roller. The take-up roller 17 takes up the substrate 1c by rotating counterclockwise (see the arrow in FIG. 2) by a drive motor (not shown).

  The substrate 1a fed from the feed roller 10 is appropriately wound around the transport rollers 11 to 14 and the first and second film forming rollers 15 and 16 between the feed roller 10 and the take-up roller 17. It is conveyed by the rotation of each of these rollers while maintaining the tension. In addition, the conveyance direction of the base materials 1a, 1b, and 1c (hereinafter, the base materials 1a, 1b, and 1c are also collectively referred to as “base materials 1a to 1c”) is indicated by arrows. The conveyance speed (line speed) of the base materials 1a to 1c (for example, the conveyance speed at the point C in FIG. 2) can be appropriately adjusted according to the type of the source gas, the pressure in the vacuum chamber 30, and the like. The conveyance speed is adjusted by controlling the rotation speeds of the drive motors of the delivery roller 10 and the take-up roller 17 by the control unit 41. When the conveyance speed is decreased, the thickness of the formed region is increased.

  The conveyance speed (line speed) of the base material can be appropriately adjusted according to the type of source gas, the pressure in the chamber, etc., but is preferably in the range of 0.25 to 100 m / min. More preferably, it is within the range of 5 to 20 m / min. If the line speed is within the above range, wrinkles due to the heat of the resin base material hardly occur, and the thickness of the formed gas barrier layer can be sufficiently controlled.

  When this film forming apparatus is used, the transport direction of the base materials 1a to 1c is set to a direction (hereinafter referred to as a reverse direction) opposite to a direction indicated by an arrow in FIG. 2 (hereinafter referred to as a forward direction). A gas barrier film forming step can also be performed. Specifically, the control unit 41 rotates the rotation directions of the drive motors of the feed roller 10 and the take-up roller 17 in the direction opposite to that described above in a state where the substrate 1c is taken up by the take-up roller 17. Control to do. When controlled in this way, the base material 1 c sent out from the take-up roller 17 is transferred to the transport rollers 11 to 14, the first and second film forming rollers 15 and 16 between the send-out roller 10 and the take-up roller 17. It is conveyed in the reverse direction by rotation of each of these rollers, maintaining appropriate tension by being wound.

  When the gas barrier layer is formed using the film forming apparatus 100, the gas barrier layer forming (film forming) step is performed by transporting the substrate 1a in the forward direction and the reverse direction and reciprocating the film forming unit S. It can be repeated multiple times.

  The gas supply pipe 18 supplies a film forming gas such as a plasma CVD source gas into the vacuum chamber 30. The gas supply pipe 18 has a tubular shape that extends in the same direction as the rotation axes of the first film forming roller 15 and the second film forming roller 16 above the film forming section S, and is provided at a plurality of locations. A film forming gas is supplied to the film forming part S from the opened opening. When the film forming apparatuses are connected (tandem type), the film forming gas supplied from the gas supply pipe 18 may be the same for each film forming apparatus, but may be different. Further, the supply gas pressure supplied from these gas supply pipes may be the same or different.

  A silicon compound can be used as the source gas. Examples of the silicon compound include hexamethyldisiloxane (HMDSO), 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, and diethylsilane. Propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, dimethyldisilazane, trimethyldisilazane, tetramethyldisilazane, pentamethyldisilazane, hexamethyldisilazane, and the like. In addition to this, the compounds described in paragraph “0075” of JP2008-056967 A can also be used. Among these silicon compounds, it is preferable to use HMDSO in the formation of the gas barrier layer from the viewpoint of easy handling of the compound and high gas barrier properties of the obtained gas barrier film. Two or more of these silicon compounds may be used in combination. The source gas may contain monosilane in addition to the silicon compound.

  As the film forming gas, a reactive gas may be used in addition to the source gas. As the reaction gas, a gas that reacts with the raw material gas to become a silicon compound such as oxide or nitride is selected. As a reactive gas for forming an oxide as a thin film, for example, oxygen gas or ozone gas can be used. In addition, you may use these reaction gas in combination of 2 or more type.

  As the film forming gas, a carrier gas may be further used to supply the source gas into the vacuum chamber 30. Further, as a film forming gas, a discharge gas may be further used to generate plasma. As the carrier gas and the discharge gas, for example, a rare gas such as argon, hydrogen, or nitrogen is used.

Hereinafter, as a representative example, a system of hexamethyldisiloxane (organosilicon compound: HMDSO: (CH ₃ ) ₆ Si ₂ O :) as a source gas and oxygen (O ₂ ) as a reaction gas will be described.

A film-forming gas containing hexamethyldisiloxane (HMDSO, (CH ₃ ) ₆ Si ₂ O) as a source gas and oxygen (O ₂ ) as a reaction gas is reacted by a plasma CVD method to form silicon- When an oxygen-based thin film is formed, a reaction represented by the following reaction formula (1) occurs by the film forming gas, and a thin film made of silicon dioxide SiO ₂ is formed.

Reaction formula (1): (CH ₃ ) ₆ Si ₂ O + 12O ₂ → 6CO ₂ + 9H ₂ O + 2SiO ₂
In such a reaction, the amount of oxygen required to completely oxidize 1 mol of hexamethyldisiloxane is 12 mol. Therefore, in the initial stage of film formation, a silicon dioxide film having a high oxygen atom ratio and a uniform composition can be obtained by completely reacting by adding 12 mol or more of oxygen to 1 mol of hexamethyldisiloxane in the film forming gas. However, the non-complete reaction is performed by controlling the gas flow rate ratio of the raw material during the film formation to the later stage to a flow rate equal to or lower than the theoretical reaction raw material ratio, and the SiO _{x according to the} present invention is performed. it is possible to increase the proportion of C _y.

  In the actual reaction in the chamber of the plasma CVD apparatus, the raw material hexamethyldisiloxane and the reaction gas, oxygen, are supplied from the gas supply unit to the film formation region to form a film. Even if the molar amount (flow rate) is 12 times the molar amount (flow rate) of the starting hexamethyldisiloxane, the reaction cannot actually proceed completely, and oxygen content It is considered that the reaction is completed only when the amount is supplied in a large excess compared to the stoichiometric ratio. For example, in order to obtain silicon oxide by complete oxidation by a CVD method, the molar amount (flow rate) of oxygen may be about 20 times or more the molar amount (flow rate) of hexamethyldisiloxane as a raw material. Therefore, the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of the raw material hexamethyldisiloxane is preferably an amount of 12 times or less (more preferably 10 times or less) which is the stoichiometric ratio. . By containing hexamethyldisiloxane and oxygen in such a ratio, carbon atoms and hydrogen atoms in hexamethyldisiloxane that have not been completely oxidized are taken into the gas barrier layer to form a desired gas barrier layer. This makes it possible to exhibit excellent gas barrier properties and bending resistance in the obtained gas barrier film. If the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of hexamethyldisiloxane in the deposition gas is too small, unoxidized carbon atoms and hydrogen atoms will be excessively taken into the gas barrier layer. become.

  The magnetic field generators 20 and 21 are members that form a magnetic field in the film forming unit S between the first film forming roller 15 and the second film forming roller 16. These magnetic field generators 20 and 21 do not follow the rotation of the first and second film forming rollers 15 and 16 and are stored at predetermined positions.

  The vacuum chamber 30 seals the delivery roller 10, the transport rollers 11 to 14, the first and second film forming rollers 15 and 16, and the take-up roller 17 and maintains a decompressed state. The pressure (vacuum degree) in the vacuum chamber 30 can be appropriately adjusted according to the type of source gas. The pressure of the film forming unit S is preferably 0.1 to 50 Pa.

  The vacuum pump 40 is communicably connected to the control unit 41 and appropriately adjusts the pressure in the vacuum chamber 30 in accordance with a command from the control unit 41.

  The control unit 41 controls each component of the film forming apparatus 100. The control unit 41 is connected to the drive motors of the feed roller 10 and the take-up roller 17 and adjusts the conveyance speed of the substrate 1a by controlling the number of rotations of these drive motors. Moreover, the conveyance direction of the base material 1a is changed by controlling the rotation direction of the drive motor. The control unit 41 is connected to a film-forming gas supply mechanism (not shown) so as to be communicable, and controls the supply amount of each component gas of the film-forming gas. The control unit 41 is communicably connected to the plasma generating power source 19 and controls the output voltage and output frequency of the plasma generating power source 19. Further, the control unit 41 is communicably connected to the vacuum pump 40 and controls the vacuum pump 40 so as to maintain the inside of the vacuum chamber 30 in a predetermined reduced pressure atmosphere.

  The control unit 41 includes a CPU (Central Processing Unit), a HDD (Hard Disk Drive), a RAM (Random Access Memory), and a ROM (Read Only Memory). The HDD stores a software program describing a procedure for controlling each component of the film forming apparatus 100 to realize a method for producing a gas barrier film. When the film forming apparatus 100 is turned on, the software program is loaded into the RAM and sequentially executed by the CPU. The ROM stores various data and parameters used when the CPU executes the software program.

  The gas barrier layer may be a single layer or a laminated structure of two or more layers. When the gas barrier layer has a laminated structure of two or more layers, the respective gas barrier layers may have the same composition or different compositions. In the case of a stacked structure, it is also preferable to use a tandem film formation apparatus in which the film formation apparatuses illustrated in FIG. 2 are connected.

  As described above, the thickness of the gas barrier layer is in the range of 15 to 50 nm. If it is this range, the advantage of coexistence of productivity and gas barrier property will be acquired. The thickness of the gas barrier layer can be measured by observation with a transmission electron microscope (TEM).

[4] Adhesion layer On the gas barrier layer of the gas barrier film of the present invention, it is preferable to provide an adhesion layer for enhancing the adhesion with the QD-containing resin layer described later.

  As the adhesion layer, an adhesion layer containing an organosilicon compound having a polymerizable group is preferably formed, and the thickness of the adhesion layer is preferably 5 nm or less.

  The organosilicon compound having a polymerizable group is not particularly limited, but is preferably a silane coupling agent, such as a halogen-containing silane coupling agent (2-chloroethyltrimethoxysilane, 2-chloroethyl). Triethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, etc.), epoxy group-containing silane coupling agent [2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3 4-epoxycyclohexyl) ethyltriethoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 2-glycidyloxyethyltrimethoxysilane, 2-glycidyloxyethyltriethoxysilane, 3-glycidyloxypropyltrimethoxy Lan, 3-glycidyloxypropyltriethoxysilane, etc.], amino group-containing silane coupling agents (2-aminoethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2- [N- (2-aminoethyl) amino] ethyltrimethoxysilane, 3- [N- (2-aminoethyl) amino] propyltrimethoxysilane, 3- (2-aminoethyl) amino] propyltriethoxysilane, 3- [N -(2-aminoethyl) amino] propyl methyldimethoxysilane), mercapto group-containing silane coupling agents (such as 2-mercaptoethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane), Vinyl group-containing silane cup (Meth) acryloyl group-containing silane coupling agent (2-methacryloyloxyethyltrimethoxysilane, 2-methacryloyloxyethyltriethoxysilane, 2-acryloyloxyethyltri) Methoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, and the like.

  In these, the silane coupling agent ((meth) acryloyl group containing silane coupling agent) containing a (meth) acryloyl group is preferable.

  As the (meth) acryloyl group-containing silane coupling agent, 1,3-bis (acryloyloxymethyl) -1,1,3,3-tetramethyldisilazane, 1,3-bis (methacryloyloxymethyl) -1, 1,3,3-tetramethyldisilazane, 1,3-bis (γ-acryloyloxypropyl) -1,1,3,3-tetramethyldisilazane, 1,3-bis (γ-methacryloyloxypropyl)- 1,1,3,3-tetramethyldisilazane, acryloyloxymethylmethyltrisilazane, methacryloyloxymethylmethyltrisilazane, acryloyloxymethylmethyltetrasilazane, methacryloyloxymethylmethyltetrasilazane, acryloyloxymethylmethylpolysilazane, methacryloyloxymethyl Methylpolysila Zane, 3-acryloyloxypropylmethyltrisilazane, 3-methacryloyloxypropylmethyltrisilazane, 3-acryloyloxypropylmethyltetrasilazane, 3-methacryloyloxypropylmethyltetrasilazane, 3-acryloyloxypropylmethylpolysilazane, 3-methacryloyloxy Propylmethylpolysilazane, acryloyloxymethylpolysilazane, methacryloyloxymethylpolysilazane, 3-acryloyloxypropylpolysilazane, and 3-methacryloyloxypropylpolysilazane are preferable, and further, 1,3-bis is preferred from the viewpoint of easy compound synthesis and identification. (Acryloyloxymethyl) -1,1,3,3-tetramethyldisilazane, 1,3-bis (methacryloyloxime) ) -1,1,3,3-tetramethyldisilazane, 1,3-bis (γ-acryloyloxypropyl) -1,1,3,3-tetramethyldisilazane, 1,3-bis (γ- (Methacryloyloxypropyl) -1,1,3,3-tetramethyldisilazane is particularly preferred.

  Examples of commercially available (meth) acryloyl group-containing silane coupling agents include KBM-5103, KBM-502, KBM-503, KBE-502, KBE-503, and KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.). Can be mentioned. One of these (meth) acryloyl group-containing silane coupling agents may be used alone, or two or more thereof may be used in combination.

  As the silane coupling agent used in the present invention, the following compounds are preferably used. For the synthesis method of the silane coupling agent, reference can be made to JP-A-2009-67778.

(In the formula, R represents CH ₂ ═CHCOOCH _2. )
The adhesion layer can be formed by applying a polymerizable composition. For example, a solution obtained by dissolving the (meth) acryloyl group-containing compound in an appropriate solvent is applied to the surface of the gas barrier layer and dried. A method is illustrated. At this time, a suitable photopolymerization initiator is added to the solution, and the coating obtained by applying the solution and drying is subjected to a light irradiation treatment, and a part of the (meth) acryloyl group-containing compound. May be polymerized to form a polymerizable polymer.

  Arbitrary appropriate methods may be employ | adopted as a method of apply | coating a coating composition. Specific examples include spin coating, roll coating, flow coating, ink jet, spray coating, printing, dip coating, cast film formation, bar coating, and gravure printing.

  Moreover, it can also form into a film by a vapor-phase film-forming method, and a vapor-phase film-forming method can be used by a well-known method. The vapor deposition method is not particularly limited. For example, physical vapor deposition (PVD) methods such as sputtering, vapor deposition, ion plating, ion assisted vapor deposition, plasma CVD, ALD (Atomic Layer Deposition). ) Method and the like. Of these, the plasma CVD method is preferable.

  The thickness of the adhesion layer may be an adhesion effect and is preferably 5 nm or less from the viewpoint of thinning. The thickness of the adhesion layer can be measured by a transmission electron microscope (TEM).

  In addition, it is preferable to add a surface treatment step between the gas barrier layer and the adhesion layer, and the surface treatment step is performed with an apparatus used for forming the gas barrier layer after forming the gas barrier layer. From the viewpoint of productivity.

  A known method can be applied to the surface treatment step, and corona treatment, plasma treatment, sputtering treatment, flame treatment, and the like can be employed. Among them, oxygen plasma treatment includes a resin base material and a gas barrier layer. Can be reduced, and can be carried out continuously with the apparatus used for forming the gas barrier layer, which is preferable in production.

[5] QD-containing resin layer Hereinafter, quantum dots (QD), resins, and the like, which are main components of the QD-containing resin layer, will be described.

<Quantum dots>
In general, semiconductor nanoparticles exhibiting a quantum confinement effect with a nanometer-sized semiconductor material are also referred to as “quantum dots”. Such a quantum dot is a small lump within about 10 and several nanometers in which several hundred to several thousand semiconductor atoms are gathered, but when absorbing energy from an excitation source and reaching an energy excited state, the energy of the quantum dot Releases energy corresponding to the band gap.

  Therefore, it is known that quantum dots have unique optical characteristics due to the quantum size effect. Specifically, (1) By controlling the size of the particles, various wavelengths and colors can be emitted. (2) The absorption band is wide and fine particles of various sizes can be obtained with a single wavelength of excitation light. It has the characteristics that it can emit light, (3) it has a symmetrical fluorescence spectrum, and (4) it has excellent durability and fading resistance compared to organic dyes.

  The quantum dots contained in the QD-containing resin layer may be known, and can be generated using any method known to those skilled in the art. For example, suitable QDs and methods for forming suitable QDs include US Pat. No. 6,225,198, US 2002/0066401, US Pat. No. 6,207,229, US Pat. No. 6,322,901. Description, US Pat. No. 6,949,206, US Pat. No. 7,572,393, US Pat. No. 7,267,865, US Pat. No. 7,374,807, US Patent Application No. 11/299299, and US Pat. No. 6,861,155 Can be mentioned.

  The QD is generated from any suitable material, preferably an inorganic material and more preferably an inorganic conductor or semiconductor material. Suitable semiconductor materials include any type of semiconductor, including II-VI, III-V, IV-VI and IV semiconductors.

Suitable semiconductor materials include Si, Ge, Sn, Se, Te, B, C (including diamond), P, BN, BP, BAs, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb. , InN, InP, InAs, InSb, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdSeZn, CdTe, HgS, HgSe, HgTe, BeS, BeSe , BeTe, MgS, MgSe, GeS, GeSe, GeTe, SnS, SnSe, SnTe, PbO, PbS, PbSe, PbTe, CuF, CuCl, CuBr, CuI, Si ₃ N ₄ , Ge ₃ N ₄ , Al ₂ O ₃ , _{(Al, Ga, In) 2} (S, Se, Te) 3, Al 2 O, and include but are more than one suitable combination of such semiconductor, and the like.

  In the present invention, the following core / shell type quantum dots, for example, CdSe / ZnS, InP / ZnS, PbSe / PbS, CdSe / CdS, CdTe / CdS, CdTe / ZnS and the like can be preferably used.

<resin>
Resin can be used for a QD containing resin layer as a binder holding a quantum dot. For example, polycarbonate, polyarylate, polysulfone (including polyethersulfone), polyester such as polyethylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate Cellulose esters such as pionate and cellulose acetate butyrate, polyvinylidene chloride, polyvinyl alcohol, ethylene vinyl alcohol, syndiotactic polystyrene, norbornene, polymethylpentene, polyether ketone, polyether ketone imide And acrylic resins such as polyamide resins, fluororesins, nylon resins, and polymethyl methacrylate.

  The QD-containing resin layer preferably has a thickness in the range of 50 to 200 μm.

  The optimum amount of quantum dots in the QD-containing resin layer varies depending on the compound used, but is generally preferably in the range of 15 to 60% by volume.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "mass part" or "mass%" is represented.

Example 1
<Manufacture of gas barrier film>
[Resin substrate]
A 125 μm-thick polyethylene terephthalate film (Lumirror (registered trademark) (UH13) manufactured by Toray Industries, Inc.) with an easy-adhesion layer formed on both sides was used. Was on the side.

[Formation of underlayer]
The underlayer was formed by applying a coating solution as shown below to form a coating film, and then performing modification by irradiation with vacuum ultraviolet rays.

  The coating solution was prepared as follows.

  Coating solution 1: a dibutyl ether solution containing 20% by mass of perhydropolysilazane (manufactured by AZ Electronic Materials, NN120-20) and an amine catalyst (N, N, N ′, N′-tetramethyl-1,6- Dihydrohexane (TMDAH))-containing perhydropolysilazane 20 mass% dibutyl ether solution (manufactured by AZ Electronic Materials Co., Ltd., NAX120-20) is mixed at a ratio of 4: 1 (mass ratio), and further dried film A coating solution was prepared by appropriately diluting with dibutyl ether to adjust the thickness.

  Coating solution 2: 2,4,6,8-tetramethylcyclotetrasiloxane was added so that the solid content ratio when preparing the coating solution 1 was 10 parts by mass with respect to 100 parts by mass of polysilazane. A coating solution was prepared by stirring at 25 ° C. for 6 hours.

  Coating solution 3: Aluminum ethyl acetoacetate diisopropylate (ALCH) was added to polysilazane so that the Al / Si ratio was 0.01 when preparing the coating solution 1, and the mixture was heated at room temperature (25 ° C.) for 6 hours. A coating solution was prepared by stirring.

  Coating liquid 4: Aluminum ethyl acetoacetate diisopropylate (ALCH) was added to polysilazane so that the Al / Si ratio was 0.03 when preparing the coating liquid 1, and the mixture was heated at room temperature (25 ° C.) for 6 hours. A coating solution was prepared by stirring.

  Coating solution 5: Polysiloxane oligomer: X-40-9225 (manufactured by Shin-Etsu Chemical Co., Ltd.) and organoaluminum curing agent: DX-9740 (manufactured by Shin-Etsu Chemical Co., Ltd.) at a ratio of 95: 5 (mass ratio). It mixed and the coating liquid was prepared.

  The obtained coating solution was applied onto the resin substrate by a die coating method so that the thickness after drying was as shown in Table 1 below, and the temperature shown in Table 1 below (dew point 5) was obtained in the air. And dried for 2 minutes. Next, the coating film obtained by drying was subjected to a vacuum ultraviolet ray irradiation treatment (modification treatment) using a Xe excimer lamp having a wavelength of 172 nm in a nitrogen atmosphere under the conditions shown in Table 1 below to form an underlayer. Formed. Further, a base layer not using the above coating solution as shown in Table 1 was also formed.

  The layer containing polysilazane was modified under the following conditions.

<Modification processing equipment>
Excimer irradiation device MODEL: MECL-M-1-200 manufactured by M.D.Com
Wavelength: 172nm
Lamp filled gas: Xe
<Reforming treatment conditions>
Excimer light intensity: 130 mW / cm ² (172 nm)
Distance between sample and light source: 2mm
Stage heating temperature: 80 ° C. (120 ° C. in film formation condition U8)
Oxygen concentration in the irradiation device: 0.3% by volume
Stage transport speed during excimer light irradiation: 10 mm / sec Stage transport count during excimer light irradiation: 3 reciprocations [Formation of gas barrier layer]
A gas barrier layer was formed on the underlayer by a vacuum plasma CVD method.

  A type in which two apparatuses each having a film forming unit composed of opposing film forming rolls shown in FIG. 2 are connected (FIG. 3: a tandem CVD film forming apparatus having a first film forming unit and a second film forming unit. The reference numerals with “′” are the same as those in FIG. 2, respectively))). The effective film formation width is 1000 mm, and the film formation conditions are as follows: transfer speed, supply amount of source gas (HMDSO) of each of the first film formation unit and the second film formation unit, supply amount of oxygen gas, degree of vacuum, and applied power It was adjusted. The number of film formation (the number of passes of the apparatus) was 1 pass. As other conditions, the power supply frequency was 84 kHz, and the film forming roll temperatures were all 10 ° C. The film thickness was determined by cross-sectional TEM observation.

  Table 2 shows the film forming conditions.

  Gas barrier films 1 to 19 as shown in Table 3 were prepared by a combination of the above-described underlayer and gas barrier layer.

  The composition distribution in the thickness direction of the above underlayer and gas barrier layer was determined by measurement by a method using the following XPS (photoelectron spectroscopy) analysis.

(XPS analysis conditions)
・ Equipment: ULVAC-PHI QUANTERASXM
・ X-ray source: Monochromatic Al-Kα
Measurement area: Si2p, C1s, N1s, O1s
・ Sputtering ion: Ar (2 keV)
Depth profile: after 1 minute sputtering, the measurement is repeated ※ corresponds to the thickness of about 2.8nm in the etching rate of SiO ₂ in terms and quantitative: seeking background Shirley method, the relative sensitivity coefficient method from the peak area obtained with And quantified. For data processing, MultiPak manufactured by ULVAC-PHI was used.

  For the underlayer, the composition distribution was measured only with the underlayer, and the average value of the composition distribution in the film thickness direction was determined. For the gas barrier layer, the composition distribution was measured with a sample laminated with the underlayer, and the average value of the composition distribution in the film thickness direction was determined. The boundary between the underlayer and the gas barrier layer was judged by comparing with the data obtained by measuring the composition distribution with only the underlayer. These results are shown in Table 3.

"Evaluation method"
<Gas barrier properties>
The gas barrier property was measured in accordance with the Mocon method (JISK7129-1992) method, and was measured under the conditions of 38 ° C. and 100% RH using a water vapor permeability measuring device Aquatran manufactured by Mocon. The results are shown in Table 3.

<Optical characteristics: light absorption at 450 nm>
Using a spectrocolorimeter CM-3500d manufactured by Konica Minolta, light transmittance (%) and light reflectance (%) at 450 nm were measured. At this time, the measurement was taken as the transmittance from the side of the gas barrier film where the gas barrier layer was formed to the back side of the substrate. The light absorptance was calculated as 100− (transmittance (%) + reflectance (%). The measurement was performed at five points in the in-plane position of the sample, and the average value was obtained.

  The gas barrier films 4, 5, 7, 8, 10 to 12, 14, 15, and 18 having the configuration of the present invention have a small light absorption rate in the vicinity of the light wavelength of 450 nm compared to the comparative example, and are excellent in gas barrier properties. I understand that.

Example 2
Using the gas barrier film produced in Example 1, a QD sheet was produced according to the following procedure.

<Formation of adhesion layer>
On the gas barrier layer of the gas barrier film sample shown in Table 4, an adhesion layer was formed as follows.

(Surface hydrophilization treatment 1: oxygen plasma treatment)
The sample cut into a sheet was processed using an atmospheric pressure plasma apparatus (manufactured by Well Co., Ltd.). Nitrogen gas was introduced as a discharge gas, the oxygen concentration was controlled to 1% by volume, and the surface hydrophilization treatment (oxygen plasma treatment) of the exposed surface of the inorganic barrier layer was performed under conditions of a frequency of 5 kHz and an applied power of 5 kV.

(Surface hydrophilization treatment 2: oxygen plasma treatment using a CVD apparatus)
After forming the gas barrier layer using the CVD apparatus used for forming the gas barrier layer, oxygen plasma treatment was subsequently performed by a roll-to-roll method. Only the first film forming unit was used, the conveyance speed was 40 m / min, the source gas was not supplied, the oxygen gas supply amount was 2000 sccm, the degree of vacuum was 2 Pa, and the applied power was 3 kW.

(Adhesion layer formation: acryloyl group-containing silane coupling agent)
KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) which is an acryloyl group-containing silane coupling agent was diluted with propylene glycol monomethyl ether (PGME) to a solid content concentration of 1% to prepare a coating solution for forming an adhesive layer. Next, this adhesive layer forming coating solution was applied to the exposed surface of the gas barrier layer with a bar coater so that the dry film thickness was 15 nm as a theoretical value, and then dried at 80 ° C. for 1 minute as a drying condition. Thus, an adhesive layer was formed. Although the dry film thickness of the adhesive layer was measured by TEM observation, the thickness could not be specified, and was estimated to be 5 nm or less. The conditions used for TEM observation are as follows.

(Conditions for TEM observation)
Device: JEOL JEM-2010F
Accelerating voltage: 200kV
Pretreatment: flake processing by FIB processing.

<Gas barrier properties after formation of adhesive layer>
Similarly, the measurement was performed under the conditions of 38 ° C. and 100% RH using a water vapor permeability measuring device manufactured by Mocon, Aquatran. The results are shown in Table 4. There was no change in gas barrier properties due to the formation of the adhesive layer.

<Production of QD sheet>
[Production of QD sheets 1 to 20]
Resin A was prepared by adding 3% polymerization initiator (BASF Japan, Irgacure 184) to pentaerythritol diacrylate, which is a polyfunctional acrylate compound, with respect to 100% of the resin amount.

  On the other hand, semiconductor nanoparticles (CdSe / ZnS) emitting red and green light were respectively synthesized according to the method described in JP-T-2013-505347. The semiconductor nanoparticles were dispersed in a toluene solvent so that the red component and the green component were 0.75 mg and 4.12 mg, respectively. The resin A prepared above was added to this dispersion to prepare a coating solution for forming an acrylic resin-containing light emitting layer in which the content of semiconductor nanoparticles was 1% (solid content).

The acrylic resin-containing light emitting layer forming coating solution prepared above was applied on each adhesive layer of the gas barrier film prepared above to form a quantum dot (QD) -containing coating film. Next, the same gas barrier film is placed so that the adhesive layer side is in contact with the quantum dot (QD) -containing coating film (two gas barrier films sandwich the quantum dot (QD) -containing coating film), and 800 mW / cm ^2. Quantum dot (QD) -containing coating film is cured by applying an ultraviolet irradiation treatment with a high-pressure mercury lamp under the condition of 300 mJ / cm ² , and acrylic resin-containing light emission corresponding to each of the gas barrier films 1 to 19 QD sheets 1 to 19 having a layer (QD-containing resin layer) were produced. In addition, the film thickness of the acrylic resin containing light emitting layer (QD containing resin layer) was 100 micrometers.

  The QD sheet 20 was subjected to surface hydrophilization treatment 2 when forming the adhesion layer.

≪Evaluation of QD sheet≫
<Peel strength of QD sheet>
About QD sheets 1-20 produced above, peel strength in each sample was measured. In addition, the sample cut each QD sheet into a size of 1 inch in length and 20 cm in width, and measured peel strength in the vertical direction using a peel tester FGPX-0.5 manufactured by SHIMPO. The measurement was performed immediately after producing the QD sheet and after leaving it for 500 hours under high temperature and high humidity conditions (60 ° C., 90% RH). The results are shown in Table 4 below. One inch is 2.54 cm.

<Brightness of QD sheet>
The QD sheet produced above was measured for luminance. The luminance is measured by placing the evaluation sample on a blue LED having an emission wavelength of 450 nm and measuring the luminance (L ^* ) using a spectral radiance meter CS-2000 (manufactured by Konica Minolta) with a height fixed to 10 cm. It went by. As for the luminance, the luminance of the QD sheet 1 was set to 100, and the relative values are shown in Table 4.

  Since the QD sheet using the gas barrier films 4, 5, 7, 8, 10 to 12, 14, 15, 18 of the configuration of the present invention is excellent in peel strength immediately after production and after high temperature and high humidity, Excellent interlayer adhesion of all layers between the base layer, the base layer, the gas barrier layer, and the gas barrier layer to the QD-containing resin layer, and the light absorption in the vicinity of the light wavelength of 450 nm is small, indicating that the luminance of the QD sheet is excellent. .

F Gas barrier film 1 Resin 2 Base layer 3 Gas barrier layer G QD sheet 4 Adhesion layer 5 QD-containing resin layer S Deposition space 1a Resin substrate 1b, 1c, 1d, 1e Deposited substrate 10 Feeding roller 11 , 12, 13, 14 Conveying roller 15 First film forming roller 16 Second film forming roller 17 Winding roller 18 Gas supply pipe 19 Power source for generating plasma 20, 21 Magnetic field generator 30 Vacuum chamber 40 Vacuum pump 41 Control unit 100 Film device 101 Film formation device (tandem type)

Claims (11)

A gas barrier film having a base layer and a gas barrier layer formed in contact with the base layer on a resin substrate, wherein the base layer and the gas barrier layer satisfy the following requirements: the film.
Underlayer: When the average composition is expressed by SiO _v C _w (where v and w are stoichiometric coefficients), 1.7 ≦ v ≦ 2.1, 0.01 ≦ w ≦ 0.2, and thickness Is in the range of 50 to 200 nm.
Gas barrier layer: When the average composition is expressed by SiO _x C _y (x and y are stoichiometric coefficients), 1.6 ≦ x ≦ 1.9, 0.15 ≦ y ≦ 0.40, and 4 ≦ 2x + 2y <4.3, and the thickness is in the range of 15 to 50 nm. The gas barrier film according to claim 1, wherein the gas barrier layer further satisfies the following requirements.
Gas barrier layer: product of y and thickness (nm) is in the range of 4-12.   The said underlayer contains metal M other than Si, and M / Si ratio (molar ratio) exists in the range of 0.001-0.05, The Claim 1 or Claim 2 characterized by the above-mentioned. Gas barrier film.   The gas barrier film according to any one of claims 1 to 3, further comprising an adhesion layer containing an organosilicon compound having a polymerizable group on the gas barrier layer.   The gas barrier film according to claim 4, wherein the adhesion layer has a thickness of 5 nm or less. A method for producing a gas barrier film in which a coating layer containing polysilazane is formed as a base layer on a resin substrate, and a chemical vapor deposition layer is formed as a gas barrier layer in contact therewith, wherein the base layer and the gas barrier A method for producing a gas barrier film, wherein the layer satisfies the following requirements.
Underlayer: When the average composition is expressed by SiO _v C _w (where v and w are stoichiometric coefficients), 1.7 ≦ v ≦ 2.1, 0.01 ≦ w ≦ 0.2, and thickness Is in the range of 50 to 200 nm.
Gas barrier layer: When the average composition is expressed by SiO _x C _y (x and y are stoichiometric coefficients), 1.6 ≦ x ≦ 1.9, 0.15 ≦ y ≦ 0.40, and 4 ≦ 2x + 2y <4.3, and the thickness is in the range of 15 to 50 nm. The method for producing a gas barrier film according to claim 6, wherein the gas barrier layer further satisfies the following requirements.
Gas barrier layer: product of y and thickness (nm) is in the range of 4-12. The gas barrier according to claim 6 or 7, wherein the gas barrier layer further contains a metal M other than Si, and the M / Si ratio is in the range of 0.001 to 0.05. For producing a conductive film.   The gas barrier film according to any one of claims 6 to 8, wherein an adhesion layer containing an organosilicon compound having a polymerizable group is further formed on the gas barrier layer. Production method.   The method for producing a gas barrier film according to claim 9, wherein a surface treatment step is added between the gas barrier layer and the adhesion layer.   The method for producing a gas barrier film according to claim 10, wherein the surface treatment step is performed by an apparatus used for forming the gas barrier layer after the gas barrier layer is formed.

Images