WO2017099239A1 - Gas barrier film and method for producing same - Google Patents

Abstract

[Problem] To provide a means for improving the gas barrier properties, the heat and humidity resistance, and the processing suitability of a gas barrier film. [Solution] A gas barrier film obtained by positioning, in order, an underlayer and a gas barrier layer next to each other on at least one surface of a resin substrate, wherein, if the average composition of the gas barrier layer is represented by SiO_xC_y (where x and y are stoichiometric coefficients): y is set to 0.40 < y ≤ 0.95; the thickness of the gas barrier layer is set to 5–90 nm; the surface hardness (SH) of the film surface on the side where the gas barrier layer is positioned with respect to the underlayer is set to 1.4–3.5 GPa, as measured by nano-indentation; and the surface roughness (Ra) of the film surface on the side where the gas barrier film is positioned with respect to the underlayer is set to 1–18 nm.

Description

Gas barrier film and method for producing the same

The present invention relates to a gas barrier film and a method for producing the same.

In the fields of food, packaging materials, pharmaceuticals, etc., a relatively simple transmission of water vapor, oxygen, etc., where a vapor deposition film made of an inorganic compound such as a metal oxide or a coating film made of a resin has been provided on the surface of a resin substrate. There is known a gas barrier film provided with a gas barrier layer (inorganic barrier layer) for preventing the above. In recent years, in the field of electronic devices such as liquid crystal display elements (LCD), solar cells (PV), organic electroluminescence (EL), quantum dots (QD), etc., the purpose is to make them light and difficult to break. There is an increasing demand for gas barrier films using a resin base material.

Conventionally, as a gas barrier layer used for a gas barrier film, a technique for providing a layer containing a compound having a SiO _{x Cy} composition by a chemical vapor deposition method (CVD method) on the surface of a resin base material has been studied. Has been. For example, in JP 2011-178064 A, an anchor layer and SiO _x C _y (1.5 ≦ x ≦ 2.0, 0 ≦ y ≦ 0.5) are expressed on the surface of the resin base material layer. A gas barrier layer having a composition and an overcoat layer are formed in sequence, and the thicknesses of the anchor layer, the gas barrier layer, and the overcoat layer are controlled so that the refractive indexes of these four layers become smaller in order. Techniques for controlling the thickness to 10 to 100 nm have been proposed. In Example 1 of JP 2011-178064 A, SiO _1.8 C _0.05 is formed on the surface of the anchor layer provided on the resin base material layer. And a gas barrier layer having a thickness of 60 nm is provided, and an overcoat layer is further provided on the gas barrier layer. According to Japanese Patent Application Laid-Open No. 2011-178064, such a configuration can improve gas barrier properties and durability.

However, according to the study by the present inventors, the gas barrier film having the structure described in Example 1 of JP 2011-178064 A may not have sufficient process suitability (abrasion resistance) during film production. found. That is, when the gas barrier film is produced (for example, roll-to-roll), the film is conveyed between the processes. At that time, the surface of the gas barrier layer is damaged, or the winding core ( It has been found that the gas barrier layer on the side close to the core) is damaged by tightening and the gas barrier property is lowered. The gas barrier layer is required to have a high gas barrier property, but it is preferable that the gas barrier property is not easily lowered (high wet heat resistance) even when placed in a high temperature and high humidity environment.

The present invention has been made in view of the above problems, and an object of the present invention is to provide means capable of improving gas barrier properties and wet heat resistance and improving process suitability in a gas barrier film.

The present inventors have intensively studied to solve the above problems. In the process, the cause of the insufficient process suitability of the gas barrier film having the structure described in Example 1 of JP 2011-178064 A was searched, and the amount of carbon (C) contained in the gas barrier layer was small. It has been found that this is a cause of reducing process suitability, and that the process suitability of the gas barrier film can be improved by increasing the amount of carbon (C) contained in the gas barrier layer. However, it was found that gas barrier properties and wet heat resistance may still not be sufficient by simply taking such measures, and further investigation was conducted. As a result, the surface hardness (SH; Surface Hardness) and surface roughness (Ra; center line average roughness) of the film are controlled to values within predetermined ranges, respectively, in addition to further improving process suitability, the gas barrier As a result, the present invention has been completed.

That is, the above-mentioned problem according to the present invention is solved by the following means.

1. A gas barrier film in which an underlayer and a gas barrier layer adjacent to each other are arranged in this order on at least one surface of a resin base material,
When the average composition of the gas barrier layer is expressed by SiO _x C _y (x and y are stoichiometric coefficients), y satisfies 0.40 <y ≦ 0.95,
The gas barrier layer has a thickness of 5 to 90 nm;
The surface hardness (SH) on the film surface on the side where the gas barrier layer is arranged with respect to the underlayer, measured by a nanoindentation method, is 1.4 to 3.5 GPa,
A gas barrier film having a surface roughness (Ra) of 1 to 18 nm on the surface of the film on which the gas barrier layer is disposed with respect to the underlayer;
2. 2. The gas barrier film according to 1 above, wherein the underlayer contains Si and a metal M other than Si, and the M / Si ratio (molar ratio) is in the range of 0.001 to 0.05;
3. 3. The gas barrier film according to 1 or 2 above, wherein the gas barrier layer has a thickness of 10 to 60 nm;
4). When the average composition of the underlayer is expressed by SiO _v C _w (v and w are stoichiometric coefficients), v satisfies 1.7 ≦ v ≦ 2.5, and w is 0.01 ≦ w ≦ 0. The gas barrier film according to any one of the above 1 to 3, satisfying .2;
5). 5. The gas barrier film according to any one of the above 1 to 4, further comprising an adhesion layer containing an organosilicon compound having a polymerizable group on the gas barrier layer;
6). 6. The gas barrier film according to 5 above, wherein the adhesion layer has a thickness of 5 nm or less;
7). Forming a coating film containing polysilazane on the resin base material, and applying a modification treatment to the coating film to form a base layer;
Forming a gas barrier layer using a vapor deposition method so as to be in contact with the underlayer;
A method for producing a gas barrier film comprising
When the average composition of the gas barrier layer is expressed by SiO _x C _y (x and y are stoichiometric coefficients), y satisfies 0.40 <y ≦ 0.95,
A method for producing a gas barrier film, wherein the gas barrier layer has a thickness of 5 to 90 nm;
8). The method for producing a gas barrier film according to 7 above, further comprising a step of forming an adhesion layer containing an organosilicon compound having a polymerizable group on the gas barrier layer after the step of forming the gas barrier layer;
9. 9. The method for producing a gas barrier film according to 8, further comprising a step of performing a surface treatment on the exposed surface of the gas barrier layer after the step of forming the gas barrier layer and before the step of forming the adhesion layer. ;
10. 10. The method for producing a gas barrier film according to 9 above, wherein the surface treatment is performed using an apparatus used for forming the gas barrier layer.

It is sectional drawing which shows the example of the gas barrier film which concerns on one Embodiment of this invention. It is sectional drawing which shows the example of the QD sheet using the gas barrier film which concerns on one Embodiment of this invention. It is a schematic diagram which shows an example of the vacuum plasma CVD apparatus used for formation of the CVD layer which is preferable embodiment of the gas barrier layer based on this invention. It is a schematic diagram which shows another example (form employ | adopted in the Example) of a vacuum plasma CVD apparatus.

One form of the present invention, at least one surface of the resin base material, a gas barrier film underlayer and the gas barrier layer are arranged in this order adjacent to each other, SiO the average composition of the gas barrier layer _x C _y (X and y are stoichiometric coefficients), y satisfies 0.40 <y ≦ 0.95, the thickness of the gas barrier layer is 5 to 90 nm, and is measured by a nanoindentation method. The surface hardness (SH) of the film surface on the side where the gas barrier layer is disposed with respect to the underlayer is 1.4 to 3.5 GPa, and the side on which the gas barrier layer is disposed with respect to the underlayer This is a gas barrier film having a surface roughness (Ra) of 1 to 18 nm on the film surface. According to the present invention, in a gas barrier film, it is possible to improve gas barrier properties and wet heat resistance and also improve process suitability.

Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In the present application, “˜” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

《Gas barrier film》
The “gas barrier property” as used in the present invention means a water vapor permeability (temperature: 38 ° C., relative humidity (RH): 100%) measured by a method based on the JIS K 7129-1992 method 1 × 10 ⁻¹ g. It means less than / m ² · day.

1A and 1B are cross-sectional views showing a configuration example of a gas barrier film according to the present invention. Specifically, FIG. 1A shows a minimum configuration of a gas barrier film F of the present invention in which a base layer 2 is laminated 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 laminated on the gas barrier layer 3 shown in FIG. 1A and a QD-containing resin layer 5 is laminated thereon. Although other functional layers are not shown in FIGS. 1A and 1B, an antistatic layer, a backcoat layer, a bleedout prevention layer, a hardcoat layer, and the like may be appropriately laminated. 1A and 1B, the base layer 2 and the gas barrier layer 3 are laminated on one side of the resin base material 1, but the base layer 2 and the gas barrier layer 3 are laminated on both sides of the resin base material 1. It may be.

[1] Resin base material As the resin base material used in the gas barrier film according to the present invention, a plastic film is preferable. 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 resin constituting the plastic film include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide resin, fluorinated polyimide resin, polyamide resin, and polyamideimide. Resin, polyetherimide resin, cellulose acylate resin, polyurethane resin, polyether ether ketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyether sulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring modified polycarbonate Examples thereof include thermoplastic resins such as resins, alicyclic modified polycarbonate resins, fluorene ring modified polyester resins, and acryloyl compounds.

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

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

[2] Underlayer The underlayer is a layer interposed between the resin base material and the gas barrier layer in the gas barrier film according to the present invention, and the specific configuration thereof is not particularly limited. However, in the present invention, it is essential that the surface hardness (SH) and the surface roughness (Ra) on the film surface on the side where the gas barrier layer described later is disposed are values within a predetermined range. And since the surface state of the underlayer also affects the surface state of the film surface, in order to satisfy the provisions of the present invention, the underlayer also has a certain degree of surface hardness and surface roughness. Must be small to some extent.

<Structure of the underlayer>
The specific composition of the underlayer is not particularly limited, but from the viewpoint described above, the underlayer is preferably a layer containing a silicon oxide compound (compound having a Si—O bond). More specifically, when the average composition of the underlayer is expressed by SiO _v C _w (v and w are stoichiometric coefficients), v satisfies 1.7 ≦ v ≦ 2.5, and w is It is preferable to satisfy 0.01 ≦ w ≦ 0.2. Here, if v is 1.7 or more, the remaining amount of N does not increase excessively, the amount of outgas of ammonia or hydrogen during the formation of the gas barrier layer is reduced, the deterioration of the gas barrier layer, and the gas barrier associated therewith. Deterioration is prevented. Further, if v is 2.5 or less, the residual amount of Si—OH does not increase excessively, the amount of outgassing of water vapor during the formation of the gas barrier layer is reduced, the deterioration of the gas barrier layer and the accompanying gas barrier properties Is prevented. Similarly, if w is 0.01 or more, the film strength and flexibility of the underlayer are sufficiently secured, and if w is 0.2 or less, the transparency of the gas barrier film is sufficiently secured.

Note that the average composition of the underlayer (SiO _v C _w ) and the average composition of the gas barrier layer (SiO _x C _y ), which will be described later, are determined by X-ray photoelectron spectroscopy (XPS: Xray Photoelectron Spectroscopy). It can be determined by measuring the distribution and averaging it. In addition, about the specific method of the average composition by the said method, the method as described in the column of the below-mentioned Example shall be employ | adopted.

The underlayer 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.

There is no particular limitation on the film thickness of the underlayer (in the case of two or more layers, the total film thickness thereof), but it is preferably 50 to 200 nm. If the film thickness of the underlayer is 50 nm or more, the influence of the surface unevenness of the resin base material can be alleviated, and the gas barrier property can be improved. On the other hand, when the film thickness of the underlayer is 200 nm or less, the total amount of outgas causing substances contained in the underlayer does not increase excessively, and the deterioration of gas barrier properties due to outgassing is prevented. Moreover, in this specification, the film thickness of each layer can be calculated | required by cross-sectional TEM observation.

As described above, the surface state of the underlayer also affects the surface state of the gas barrier layer surface. Therefore, the surface of the base layer (the surface opposite to the side where the resin base material is located (in other words, the surface on which a gas barrier layer described later is formed); hereinafter also referred to as “gas barrier layer forming surface”) It is preferable to control the hardness (SH) and the surface roughness (Ra) to values within a predetermined range. Specifically, the surface hardness (SH) of the gas barrier layer forming surface of the underlayer is preferably 1.0 to 3.0 GPa, more preferably 1.5 to 3.0 GPa. Further, the surface roughness (Ra) of the gas barrier layer forming surface of the underlayer is preferably 1 to 18 nm, more preferably 1 to 6 nm. Furthermore, the surface roughness (Rz) of the gas barrier layer forming surface of the underlayer is preferably less than 30 nm. In the present specification, “surface hardness (SH)” is a value measured according to the nanoindentation method, and a value measured by the method described in the column of Examples described later is adopted. . “Surface roughness (Ra)” refers to centerline average roughness (Ra), and “surface roughness (Rz)” refers to ten-point average roughness (Rz). All of these shall adopt values measured by the method described in the column of Examples described later, in accordance with the method defined in JIS B 0601: 1994.

<Other metals>
The underlayer preferably further contains a metal M other than Si in addition to Si. In this case, the M / Si ratio (molar ratio) is preferably in the range of 0.001 to 0.05.

Examples of the metal M 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. . Of these, Al, B, Ti and Zr are preferable, and Al is particularly preferable.

<Formation method of underlayer>
There is no particular limitation on the method for forming the underlayer, and those skilled in the art can appropriately set the formation method with reference to conventionally known knowledge. Among these, from the advantages that the above-mentioned surface state can be achieved, and excellent in film formability and few defects such as cracks, the coating film formed by applying a coating liquid containing polysilazane, It is preferable to form the underlayer by applying energy and applying a modification treatment.

(Polysilazane)
Polysilazane is a polymer having a silicon-nitrogen bond, such as SiO ₂ , Si ₃ N ₄ having a bond such as Si—N, Si—H, or N—H, and ceramics such as both intermediate solid solutions SiO _x N _y. It is a precursor inorganic polymer. Examples of polysilazane include perhydropolysilazane (PHPS) and organopolysilazane. Specifically, the polysilazane preferably has the following structure.

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, examples of the alkyl group include linear, branched or cyclic alkyl groups having 1 to 8 carbon atoms. 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. Examples of the aryl group include aryl groups having 6 to 30 carbon atoms. 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 A condensed polycyclic hydrocarbon group such as an Can be mentioned. The (trialkoxysilyl) alkyl group includes 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 specific examples include 3- (triethoxysilyl) propyl group and 3- (trimethoxysilyl) propyl group. The substituent optionally present in R ₁ to R ₃ is not particularly limited, and examples thereof include 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. Note that the optionally present substituent is not the same as R ₁ to R ₃ to be substituted. 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.

In the general formula (I), n is an integer, and it is preferable that the polysilazane having the structure represented by the general formula (I) is determined to have a number average molecular weight of 150 to 150,000 g / mol.

In the compound having the structure represented by the general formula (I), one of preferred embodiments is perhydropolysilazane (PHPS) in which all of R ₁ , R ₂ and R ₃ are hydrogen atoms. An underlayer formed from such polysilazane is preferable from the viewpoint of high density and low residual organic matter.

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

Polysilazane is commercially available in a solution 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 used in combination. Moreover, you may dilute and use a commercial item with a suitable solvent. Examples of commercially available polysilazane solutions include NN120-10, NN120-20, NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL120-20, NL150A, NP110, NP140, and SP140 manufactured by Merck Co., Ltd. .

In addition, for details of polysilazane, paragraphs “0024” to “0040” of JP2013-255910A, paragraphs “0037” to “0043” of JP2013-188942A, and JP2013-2013A 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 Japanese Patent No. 226758.

In the case of using polysilazane, 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. 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.

(Compound containing metal M)
As described above, the base layer preferably contains a metal M other than Si in addition to Si. However, in order to form the base layer having such a configuration, the metal M is added to the coating liquid containing polysilazane described above. What is necessary is just to add the compound to contain and to use for formation of a base layer.

Examples of the aluminum compound applicable to the present invention include aluminum isopropoxide, aluminum-sec-butyrate, titanium isopropoxide, aluminum triethylate, aluminum triisopropylate, aluminum tritert-butylate, and aluminum tri-n-butylate. , Aluminum trisec-butyrate, aluminum ethyl acetoacetate diisopropylate, acetoalkoxyaluminum diisopropylate, aluminum diisopropylate monoaluminum-t-butylate, aluminum trisethylacetoacetate, aluminum oxide isopropoxide trimer, etc. . Specific examples of commercially available products of these compounds include AMD (aluminum diisopropylate monosec-butyrate), ASBD (aluminum secondary butyrate), ALCH (aluminum ethyl acetoacetate diisopropylate), ALCH- TR (aluminum trisethyl acetoacetate), aluminum chelate M (aluminum alkyl acetoacetate / diisopropylate), aluminum chelate D (aluminum bisethylacetoacetate / monoacetylacetonate), aluminum chelate A (W) (aluminum trisacetylacetate) Nate) (above, manufactured by Kawaken Fine Chemical Co., Ltd.), Preneact (registered trademark) AL-M (acetoalkoxyaluminum diisopropylate, Ajinomoto Fine Chemica) Etc., Ltd.) Co., Ltd., and the like.

Further, as described above, when the average composition of the underlayer is expressed by SiO _v C _w , v satisfies 1.7 ≦ v ≦ 2.5, and w satisfies 0.01 ≦ w ≦ 0.2. Although satisfy | filling is preferable, the carbon (C) contained in a base layer originates in the carbon atom contained in the compound containing polysilazane and the metal M. Therefore, as a method for controlling the amount (w) of carbon (C) contained in the underlayer within the above range, for example, the amount of compound containing polysilazane or metal M in the coating solution, the modification after coating, Examples thereof include a method of adjusting the processing energy of the quality treatment (heat treatment, UV treatment, VUV (excimer) treatment). Here, if the addition amount is increased, the C amount is also increased, but if the processing energy is increased, the C amount is decreased. In addition, when a compound containing metal M is added to the coating solution and a base layer is formed by a coating method, N contained in polysilazane is replaced with O during coating and drying, and the energy of the modification treatment after coating is low. There is also an advantage that v and w can be efficiently controlled to values within the above range.

In addition, when using the compound containing the metal M, it is preferable to mix in a coating liquid with polysilazane in inert gas atmosphere. This is to prevent the compound containing the metal M from reacting with moisture and oxygen in the atmosphere and causing violent oxidation. When the compound and polysilazane are mixed, it is preferable to raise the temperature to 30 to 100 ° C. and hold for 1 minute to 24 hours with stirring.

(solvent)
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 (for example, hydroxy group or amine group) that easily react with polysilazane. 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 may be selected according to purposes such as the solubility of the compound containing polysilazane and metal M 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 is preferably 1 to 80% by mass, more preferably 5 to 50% by mass, More preferably, it is 10 to 40% by mass.

The underlayer-forming coating solution preferably contains a catalyst in order to promote the modification of the coating film. 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 addition amount of the catalyst within 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.

In the coating solution for forming the underlayer, the following additives can be used as 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. Specifically, a compound A (siloxane compound or silsesquioxane compound having an organic group) having an Si—O bond and an organic group directly bonded to Si described in International Publication No. 2013/077255. Can be preferably used. This compound A has a reactive group such as a Si—H group or a Si—OH group, so that polysilazane is combined with a matrix that is modified by irradiation with VUV light and is integrated while locally introducing an organic group. sell. Further, by controlling the molecular weight of the compound A to 90 to 1200, the region where the organic group is introduced in the underlayer is formed in a uniformly dispersed state in a nano size, which contributes to good gas barrier properties. be able to. Moreover, the polysiloxane compound represented by the following general formula (1) described in International Publication No. 2015/041207 can also be preferably used.

In the general formula (1), the R ¹¹ are each independently a hydrogen atom, an alkyl group, is an alkenyl group, a cycloalkyl group, an aryl group, an alkoxy group, an amino group, and a group selected from the group consisting of alkylsilyl group . These groups may be substituted with one or more groups selected from the group consisting of halogen atoms, alkyl groups, alkoxy groups, amino groups, silyl groups, and alkylsilyl groups. These R ¹¹ form a side chain of polysiloxane, but preferably do not contain a highly reactive substituent in order to prevent unnecessary reaction. For this reason, an alkyl group is preferable, an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is most preferable. R ¹¹ in the formula may be a different group, but all are preferably alkyl groups, particularly methyl groups.

R ¹¹ may contain a small amount of a reactive group as long as the effects of the present invention are not impaired. Specifically, the effects of the present invention can be exhibited if the total number of amino groups and alkoxy groups contained in all R ¹¹ is 5% or less, preferably 3% or less of the total number of R ¹¹ . On the other hand, when R ¹¹ contains a hydroxyl group, a carboxyl group, or the like, a highly hydratable hydroxyl group remains in the film, and thus it is difficult to improve the gas barrier performance. Therefore, it is preferred that R ¹¹ does not contain a hydroxyl group or a carboxyl group.

R ¹² is a terminal group bonded to a silicon atom at the terminal of the polysiloxane main chain. This terminal group portion is bonded to polysilazane, stabilizes the nitrogen atom in the polysilazane, and can contribute to the realization of high gas barrier performance. Then, in order to proceed properly the reaction of the polysiloxane and polysilazane, R ¹² is required to be certain things.

Typically, R ¹² is a hydrocarbon group having 1 to 8 carbon atoms. Moreover, a part of carbon contained in such a hydrocarbon group may be substituted with nitrogen. Examples of the nitrogen-substituted hydrocarbon group include —R ¹³ —N—R ¹⁴ ₂ . Here, R ¹³ is a hydrocarbon group having 1 to 5 carbon atoms, and R ¹⁴ is independently hydrogen or a hydrocarbon group having 1 to 3 carbon atoms. As described above, R ¹² is selected to have an appropriate reactivity, and specifically, methyl group, ethyl group, propyl group, aminomethyl group, aminoethyl group, aminopropyl group, or N-ethylamino group is selected. A group selected from the group consisting of -2-methylpropyl groups is preferred. A plurality of R ¹² are contained in the polysiloxane represented by the formula (1), but they may be the same or different.

The molecular weight of the polysiloxane compound is not particularly limited, but for example, a polystyrene-equivalent weight average molecular weight is preferably in the range of 500 to 100,000, more preferably in the range of 1,000 to 50,000.

(Application method)
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 of the coating liquid (the thickness of the coating film) can be appropriately selected according to the thickness of the base layer.

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.

The drying temperature of the coating film varies depending on the substrate to be applied, but is preferably 50 to 200 ° C. For example, when a polyethylene terephthalate substrate having a glass transition temperature (Tg) of 70 ° C. is used as the resin substrate, the drying temperature is preferably set to 150 ° C. or less in consideration of deformation of the substrate due to heat.

(Energy application)
Subsequently, the coating layer containing polysilazane formed as described above is subjected to a modification treatment such as application of energy to form a base layer.

As a method for applying a modification treatment (applying energy) to a coating film containing polysilazane, 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 of 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 light (synonymous with ultraviolet light) have high oxidation ability, and can form a silicon oxide film or silicon oxynitride film having high density and insulation at low temperature. Is possible.

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.

In the ultraviolet irradiation, it is preferable to set the irradiation intensity and the irradiation time within a range in which the substrate carrying the irradiated underlayer is not damaged.

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

In general, when the substrate temperature during ultraviolet irradiation treatment is 150 ° C. or more, in the case of a plastic substrate, the properties of the substrate are impaired, such as the substrate being deformed or its strength deteriorated. 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 generated ultraviolet ray to the coating film containing polysilazane, from the viewpoint of achieving efficiency improvement and uniform irradiation, the layer containing polysilazane after reflecting the ultraviolet ray from the generation source with a reflector. Is preferred.

UV irradiation can be applied to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate used. For example, in the case of batch treatment, a laminate having a coating film containing polysilazane on the surface can be treated in an ultraviolet baking furnace equipped with the ultraviolet ray generation 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 coating film 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 the 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 the vacuum ultraviolet irradiation uses light energy of 100 to 200 nm, preferably light energy of a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the polysilazane compound, and bonds 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 preferably generates light having a wavelength of 100 to 180 nm, but more preferably an excimer radiator having a maximum emission at about 172 nm (eg, Xe excimer lamp), a low pressure having an emission line at about 185 nm. Mercury vapor lamps, as well as medium and high pressure mercury vapor lamps having a wavelength component of 230 nm or less, and excimer lamps having a maximum emission at about 222 nm.

Oxygen is required 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 tends to decrease. It is preferable to carry out in a state where the water vapor concentration is low. That is, the oxygen concentration at the time of irradiation with vacuum ultraviolet rays 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.

The gas satisfying the irradiation atmosphere used at the time of irradiation with vacuum ultraviolet rays is preferably a dry inert gas, and particularly preferably dry nitrogen gas 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 1 ~ 10W / cm ^2, more preferably ^{30 ~ 200mW / cm 2, 50} ~ More preferably, it is 160 mW / cm ² . If it is 1 mW / cm ² or more, the reduction of the reforming efficiency is prevented, and if it is 10 W / cm ² or less, generation of ablation in the coating film and damage to the substrate can be prevented.

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 to be used may be generated by plasma formed from a gas containing at least one of CO, CO ₂ and CH ₄ (hereinafter also referred to as “carbon-containing gas”). Further, as the gas containing at least one of CO, CO ₂ and CH ₄ , a carbon-containing gas may be used alone, but a rare gas or H ₂ is used as a main gas and a small amount of carbon-containing gas is added. Is preferred. Examples of plasma generation methods include capacitively coupled plasma.

[3] Gas barrier layer The gas barrier film of the present invention is a layer disposed on the surface of the underlayer opposite to the resin base so as to be adjacent to the above-described underlayer.

<Configuration of gas barrier layer>
In the present invention, the gas barrier layer is characterized in that y satisfies 0.40 <y ≦ 0.95 when the average composition is expressed by SiO _x C _y (x and y are stoichiometric coefficients). There is one.

According to the study by the present inventors, the gas barrier film having the structure described in Example 1 of JP 2011-178064 A may not have sufficient process suitability (scratch resistance) during production of the film. found. In the course of earnest study, the present inventors searched for the cause of insufficient process suitability of the gas barrier film having the structure described in Example 1 of JP2011-178064A. The fact that the amount of carbon (C) contained is a cause of reducing process suitability, and the process suitability of the gas barrier film is improved by increasing the amount of carbon (C) contained in the gas barrier layer. I found out. From such a viewpoint, the lower limit value of the y value is set to be more than 0.40. Note that the mechanism by which the process suitability is improved by increasing the amount of carbon (C) (specifically, the value of y exceeds 0.40) is not completely clear, but is included in the gas barrier layer. Presuming that the amount of carbon (C) increases, the flexibility of the gas barrier layer is improved, the surface of the gas barrier layer is less likely to be scratched, and the process suitability is affected by the scratch resistance. Yes. On the other hand, if y is 0.95 or less, the transparency of the gas barrier film is sufficiently secured, which is preferable. On the other hand, the value of x (the amount of oxygen (O) in the average composition of the gas barrier layer) is not particularly limited, but x preferably satisfies 1.4 ≦ x ≦ 1.9. If x is 1.4 or more, the transparency of the gas barrier film is sufficiently secured, which is preferable. On the other hand, if x is 1.9 or less, gas barrier properties are sufficiently secured, which is preferable.

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 gas barrier layers may have the same composition or different compositions. In addition, when the gas barrier layer has a laminated structure of two or more layers, the gas barrier layer positioned closest to the resin substrate may be adjacent to the above-described base layer.

In the present invention, the film thickness of the gas barrier layer (the total film thickness in the case of two or more layers) is 5 to 90 nm. If the thickness of the gas barrier layer is less than 5 nm, sufficient gas barrier properties cannot be obtained. On the other hand, when the film thickness of the gas barrier layer exceeds 90 nm, durability (wet heat resistance) when the gas barrier film is placed in a high temperature and high humidity environment (humid heat environment) is lowered. This is presumably because the gas barrier layer having a large film thickness cannot follow the deformation of the resin substrate during storage in a humid heat environment, and cracks are generated in the gas barrier layer. The film thickness of the gas barrier layer is more preferably 10 to 60 nm.

As described above, according to the study by the present inventors, it has been found that the process suitability of the gas barrier film can be improved by increasing the amount of carbon (C) in the average composition of the gas barrier layer. It was done. However, it has also been found that the gas barrier property and the wet heat resistance of the gas barrier film may still not be sufficient by simply taking such measures. For this reason, as a result of further studies by the present inventors, the process suitability is further improved by controlling the surface hardness (SH) and the surface roughness (Ra) of the gas barrier layer surface to values within a predetermined range, respectively. In addition, it has been found that gas barrier properties and wet heat resistance can also be improved.

That is, in the present invention, the surface hardness (SH) on the film surface on the side where the gas barrier layer is disposed with respect to the underlayer is essential to be 1.4 to 3.5 GPa, preferably 2.4 to 3.5 GPa. If the surface hardness (SH) is less than 1.4 GPa, sufficient gas barrier properties and wet heat resistance cannot be ensured. On the other hand, if the value of the surface hardness (SH) exceeds 3.5 GPa, the brittleness of the surface becomes too high, and it is liable to be damaged by winding when wound on a roll, which is not preferable. In the present invention, it is essential that the surface roughness (Ra) on the film surface on the side where the gas barrier layer is disposed with respect to the underlayer is 1 to 18 nm, preferably 1 to 7 nm. When the value of the surface roughness (Ra) is less than 1 nm, the performance is not improved. On the other hand, if the value of the surface roughness (Ra) exceeds 18 nm, sufficient gas barrier properties and wet heat resistance cannot be ensured. Furthermore, the surface roughness (Rz) on the film surface on the side where the gas barrier layer is disposed with respect to the underlayer is preferably less than 35 nm.

In addition, there is no restriction | limiting in particular about the method of controlling the surface hardness (SH) and surface roughness (Ra) in the film surface of the side by which the gas barrier layer is arrange | positioned with respect to a base layer to the value within the range mentioned above, A conventionally well-known Findings can be referred to as appropriate. As an example, as described above in the column of the underlayer, there is a method of adjusting the surface hardness (SH) and the surface roughness (Ra) on the surface of the underlayer (gas barrier layer forming surface) to values within a predetermined range. Can be mentioned. When it is assumed that the same underlayer is used, the surface hardness (SH) on the film surface can be increased by increasing the amount of oxygen (O) in the average composition of the gas barrier layer. Similarly, by increasing the film thickness of the gas barrier layer, the surface roughness (Ra) on the film surface can be reduced.

<Method for forming gas barrier layer>
The method for forming the gas barrier layer is not particularly limited, and those skilled in the art can appropriately set the formation method with reference to known knowledge. Among these, the gas barrier layer is formed by a vapor deposition method because it can achieve the above-described surface condition of the film and can easily control the amount of carbon (C) in the average composition of the gas barrier layer. It is preferable to do. As the vapor deposition method, there are a physical vapor deposition method (PVD method: Physical Vapor Deposition) and a chemical vapor deposition method (CVD method: chemical vapor deposition).

Thus, according to the present invention, it is preferable that the underlayer is formed by modifying the polysilazane-containing coating film, and the gas barrier layer is manufactured by a vapor deposition method. That is, according to another aspect of the present invention, a step of forming a coating film containing polysilazane on a resin base material, subjecting the coating film to a modification treatment to form a base layer, and the base layer, A gas barrier film forming method using a vapor phase film forming method so as to be in contact with each other, wherein an average composition of the gas barrier layer is SiO _x C _y (where x and y are stoichiometric amounts). A method for producing a gas barrier film is also provided in which y satisfies 0.40 <y ≦ 0.95 and the thickness of the gas barrier layer is 5 to 90 nm. Hereinafter, a vapor phase film forming method which is a preferable method for forming the gas barrier layer will be described.

(Vapor 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 base material, and the film is deposited by a chemical reaction on the base material surface 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 the 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 a 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 amount (x) of oxygen (O) and the amount (y) of carbon (C) in the above average composition (SiO _x C _y ) of the gas barrier layer, it is preferable to use a vacuum plasma CVD method. A desired composition can be achieved by controlling the type and supply speed of the gas, the plasma intensity, the film forming apparatus, the film forming speed, and the like. For example, the desired composition can be controlled by appropriately combining the supply amount and ratio of the film formation raw material and oxygen, the transport speed during film formation, the number of film formation, 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. 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, 16, a take-up roller 17, a gas supply pipe 18, a 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 a 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 that have a rotation axis substantially parallel to the delivery roller 10 and are opposed to 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. The temperature of the first film-forming roller 15 and the second film-forming roller 16 is not particularly limited, and is, for example, −30 to 100 ° C., but is excessively high beyond the glass transition temperature of the substrate 1a. If set, the substrate may be deformed by heat.

Magnetic field generators 20 and 21 are installed inside 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 having this configuration is, for example, 60 to 100 kHz, and the applied power is, for example, 1 to 10 kW with respect to an effective film forming width of 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 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 substrate 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 60 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 in the direction (hereinafter referred to as the reverse direction) opposite to the direction indicated by the arrow in FIG. 2 (hereinafter referred to as the 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 substrate 1c fed 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 feed 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.

In the case of forming a gas barrier layer using the film forming apparatus 100, the gas barrier layer forming (film forming) step is performed a plurality of times by transporting the substrate 1a in the forward and reverse directions and reciprocating the film forming section S. It can be repeated.

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 unit 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), tetramethylcyclotetrasiloxane (TMCTS), 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, and methylsilane. , Dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, dimethyldisilazane, trimethyldisilazane, tetramethyldisilazane, pentamethyldisilazane, hexamethyl Disilazane etc. are mentioned. In addition to these, the compounds described in paragraph “0075” of JP-A-2008-056967 can also be used. 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. the can be formed by controlling the material ratio less of the flow rate of complete response is the stoichiometric ratio of the gas flow rate ratio of the raw material in the film forming ~ late to perform the incomplete reaction, SiO _x in accordance with the present invention 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. In addition, if the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of hexamethyldisiloxane in the film forming gas is too small, unoxidized carbon atoms and hydrogen atoms are 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 maintains the decompressed state by sealing 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. 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.

[4] Adhesion layer When the gas barrier film of the present invention is used by being laminated with a QD-containing resin layer to be described later, an adhesion layer is provided on the gas barrier layer to enhance the adhesion with the QD-containing resin layer. It is preferable. In other words, the manufacturing method according to the above aspect preferably further includes a step of forming an adhesion layer containing an organosilicon compound having a polymerizable group on the gas barrier layer after the step of forming the gas barrier layer.

As the adhesion layer, it is preferable to form an adhesion layer containing an organosilicon compound having a polymerizable group, 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 agents [2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 2-glycidyloxyethyltrimethoxysilane, 2-glycidyloxyethyltriethoxysilane, 3-glycidyloxypropyltrimethoxy Silane, 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] propylmethyldimethoxysilane), mercapto group-containing silane coupling agents (such as 2-mercaptoethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane), Vinyl group-containing silane Ring agent (vinyltrimethoxysilane, vinyltriethoxysilane, etc.), (meth) acryloyl group-containing silane coupling agent (2-methacryloyloxyethyltrimethoxysilane, 2-methacryloyloxyethyltriethoxysilane, 2-acryloyloxyethyltri) Methoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, etc.).

Of these, silane coupling agents containing (meth) acryloyl groups ((meth) acryloyl group-containing silane coupling agents) are preferred.

Examples of the (meth) acryloyl group-containing silane coupling agent include 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 Methyl policy Razan, 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 (methacryloyloxy) Methyl) -1,1,3,3-tetramethyldisilazane, 1,3-bis (γ-acryloyloxypropyl) -1,1,3,3-tetramethyldisilazane, 1,3-bis (γ- Particularly preferred is methacryloyloxypropyl) -1,1,3,3-tetramethyldisilazane.

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 compounds shown below 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 method in which 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. Is exemplified. 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.

Any appropriate method can be adopted as a method of applying the 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.

Also, the adhesion layer can be formed by a vapor deposition method, and the vapor deposition method can be used by a 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 film thickness of the adhesion layer may be an adhesion effect, and is preferably 5 nm or less from the viewpoint of thinning.

Preferably, the method further includes a step of performing a surface treatment on the exposed surface of the gas barrier layer after the step of forming the gas barrier layer and before the step of forming the adhesion layer. It is preferable from the viewpoint of productivity to carry out using the apparatus used for forming the gas barrier layer.

A known method can be applied to the surface treatment process, and corona treatment, plasma treatment, sputtering treatment, flame treatment, and the like can be employed. Among these, oxygen plasma treatment is preferable in terms of production because damage to the resin base material and the gas barrier layer can be reduced and it can be carried out continuously with the apparatus used for forming the gas barrier layer.

[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 / 299,299, and US Pat. No. 6,861,155 Can be mentioned.

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, 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 two or more but include 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.

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.

<< Production of gas barrier film >>
<Resin substrate>
A 100 μm thick polyethylene terephthalate film (Lumirror (registered trademark) (U403), manufactured by Toray Industries, Inc.) having an easy-adhesion layer formed on both sides was used as a resin base material. Each layer was formed.

<Preparation of gas barrier film 1>
[Formation of clear hard coat (CHC) layer]
A clear hard coat layer was formed on the resin substrate by the following method. That is, UV curable resin OPSTAR (registered trademark) Z7527 manufactured by JSR Corporation was applied to a resin substrate so that the film thickness after drying was 3 μm (3000 nm), and then dried at 80 ° C. Thereafter, curing was performed under a condition of irradiation energy of 0.5 J / cm ² using a high-pressure mercury lamp in the air. In this way, a clear hard coat layer was formed.

[Formation of gas barrier layer]
A gas barrier layer 1 having a film thickness of 5 nm was formed on the clear hard coat layer by the following vacuum plasma CVD method to produce a gas barrier film 1. In addition, the film thickness of a gas barrier layer is the value calculated | required by cross-sectional TEM observation.

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.))) Was used. The effective film formation width is 1000 mm, and the film formation conditions include the conveyance speed, the type and supply amount of the source gas of each of the first film formation unit and the second film formation unit, the supply amount of oxygen gas, the applied power, the pressure, and the film formation. The number of times was adjusted as follows. As other conditions, the power supply frequency was 84 kHz, and the film forming roll temperatures were all 10 ° C .:
Conveyance speed: 50 m / min. Source gas (type, supply amount): HMDSO, 75 sccm
Oxygen supply amount: 530sccm
Applied power: 4kW
Pressure: 1.5Pa
Number of film formation: 1 time.

<Preparation of gas barrier film 2>
Instead of the clear hard coat layer, except that the underlayer was formed by the following method, and that each condition in the vacuum plasma CVD method when forming the gas barrier layer was changed as shown in Table 1 below, A gas barrier film 2 was prepared in the same manner as in “Preparation of gas barrier film 1” described above.

[Formation of underlayer]
First, the following coating solution 1 was prepared.

Coating solution 1: a dibutyl ether solution containing 20% by mass of perhydropolysilazane (Merck Co., Ltd., NN120-20) and an amine catalyst (N, N, N ′, N′-tetramethyl-1,6-diaminohexane ( TMDAH)) and a 20% by weight dibutyl ether solution (Merck Co., Ltd., NAX120-20) containing perhydropolysilazane in a ratio of 3: 1 (mass ratio), and further adjusting the dry film thickness. And appropriately diluted to prepare a coating solution.

The underlayer was formed by applying the coating solution 1 on a resin base material to form a coating film, and then performing modification by irradiation with vacuum ultraviolet rays. Specifically, the coating solution 1 prepared above is applied on the resin base material by a die coating method so that the thickness after drying is 60 nm, and is 80 ° C. (dew point 5 ° C.) in the air. Dried for 2 minutes. Next, the coating film obtained by drying is 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 at an irradiation energy of 0.8 J / cm ^2. Thus, an underlayer was formed. The equipment and conditions used for the reforming treatment are as follows:
<Equipment and conditions for reforming treatment>
Apparatus: Apparatus capable of performing in-line coating, drying, and modification according to the roll-to-roll method described in Japanese Patent Application Laid-Open No. 2012-116101 Distance between sample and lamp tube surface: 10 mm
Reforming zone ambient temperature: 80 ° C
Oxygen concentration in the irradiation apparatus: 0.1% by volume.

<Preparation of gas barrier film 3>
The gas barrier film 3 was prepared in the same manner as the above-described “Production of the gas barrier film 2” except that the conditions in the vacuum plasma CVD method for forming the gas barrier layer were changed as shown in Table 1 below. Produced.

<Preparation of gas barrier film 4>
First, the following coating liquid 2 was prepared.

Coating solution 2: 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). The mixture was mixed to prepare a coating solution.

When forming the base layer, the coating liquid 2 prepared as described above is used in place of the coating liquid 1, and the coating amount of the coating liquid is set so that the thickness of the base layer becomes the value shown in Table 1 below. In addition, the drying temperature of the coating film and the irradiation energy during the modification treatment were changed to the values shown in Table 1 below. Further, the conditions in the vacuum plasma CVD method when forming the gas barrier layer and the film thickness of the gas barrier layer were changed as shown in Table 1 below. Except for these points, the gas barrier film 4 was prepared in the same manner as the above-mentioned “Preparation of the gas barrier film 3”.

<Preparation of gas barrier film 5>
First, the following coating solution 3 was prepared.

Coating solution 3: Aluminum ethyl acetoacetate diisopropylate (ALCH) was added to polysilazane so that the Al / Si ratio (molar ratio) was 0.01 when preparing the coating solution 1, and room temperature (25 ° C. ) For 6 hours to prepare a coating solution.

When forming the base layer, the coating liquid 3 prepared as described above is used in place of the coating liquid 1, and the coating amount of the coating liquid is set so that the thickness of the base layer becomes the value shown in Table 1 below. In addition, the drying temperature of the coating film and the irradiation energy during the modification treatment were changed to the values shown in Table 1 below. Except for these points, the gas barrier film 5 was prepared by the same method as the above-mentioned “Preparation of the gas barrier film 4”.

<Preparation of gas barrier film 6>
A gas barrier film 6 was produced by the same method as the above-mentioned “Production of gas barrier film 5” except that an adhesion layer was formed on the exposed surface of the gas barrier layer by the following method.

(Surface hydrophilization treatment: oxygen plasma treatment using vacuum plasma CVD equipment)
After forming the gas barrier layer using the vacuum plasma CVD apparatus used for forming the gas barrier layer, oxygen plasma treatment was subsequently performed by a roll-to-roll method. At this time, only the first film forming unit was used, the transfer 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.), 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 adhesion layer. Next, this adhesion 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. An adhesion layer was formed. Although the dry film thickness of the adhesion 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 the TEM observation are as follows.

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

<Production of gas barrier films 7 to 13>
The film thickness after drying of the underlayer and the irradiation energy during the modification treatment were changed as shown in Table 1 below. Further, the conditions in the vacuum plasma CVD method when forming the gas barrier layer and the film thickness of the gas barrier layer were changed as shown in Table 1 below. Except for these points, gas barrier films 7 to 13 were prepared in the same manner as in “Preparation of gas barrier film 5” described above.

<Preparation of gas barrier film 14>
A gas barrier film 14 is formed in the same manner as in the above-mentioned “Preparation of gas barrier film 1” except that a silicon oxide (SiO ₂ ) film having a thickness of 150 nm is formed by sputtering instead of the clear hard coat layer. Was made. At the time of film formation by sputtering, polycrystalline silicon was used as a target, and film formation was performed using a roll-to-roll film formation apparatus.

<Measurement of physical properties of gas barrier film>
<Composition distribution (average composition) of underlayer and gas barrier layer>
The composition distribution in the thickness direction of the underlayer and gas barrier layer formed as described above was determined by measurement using the following XPS (photoelectron spectroscopy) analysis.

(XPS analysis conditions)
・ Device: QUANTERASXM manufactured by ULVAC-PHI
・ X-ray source: Monochromatic Al-Kα
Measurement area: Si2p, C1s, N1s, O1s
・ Sputtering ion: Ar (2 keV)
Depth profile: After sputtering for 1 minute, repeat the measurement to obtain the 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. MultiPak manufactured by ULVAC-PHI was used for data processing.

The composition distribution of the gas barrier layer was determined as an average value (average composition) of the composition distribution in the film thickness direction by measuring the composition distribution with a sample laminated with the clear hard coat layer or the base layer. Further, 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. The values of v and w when the average composition of the underlayer thus obtained is represented by SiO _v C _w and the value of y when the average composition of the gas barrier layer is represented by SiO _x C _y , It is shown in Table 1 below.

<Surface hardness (SH) of exposed surface of gas barrier layer>
The surface hardness (SH) of the exposed surface of the gas barrier layer (the exposed surface of the adhesion layer in the gas barrier film 6) was measured according to the nanoindentation method. Specifically, the measurement was performed using a scanning probe microscope (SPI3800N manufactured by Seiko Instruments Inc.) and Triscope manufactured by Hysitoron. Note that a cube corner tip (90 °) was used as the working indenter. The measurement results are shown in Table 1 below.

<Surface roughness (Ra) of exposed surface of gas barrier layer>
The surface roughness (Ra) of the exposed surface of the gas barrier layer (the exposed surface of the adhesion layer in the gas barrier film 6) was measured using a wykoNT9300 non-contact three-dimensional micro surface shape measuring system manufactured by Veeco. Here, the “surface roughness (Ra)” is a non-contact three-dimensional surface shape measuring device, and average surface roughness (centerline average roughness) when measuring 200 μm × 200 μm in a plurality of locations (5 locations or more). A). The measurement results are shown in Table 1 below. When the surface roughness (Rz; ten-point average roughness) of the surface of the base layer (gas barrier layer forming surface) was measured by the same method after forming the base layer, any of the gas barrier films 3 to 12 according to the present invention was measured. Also showed a value of less than 30 nm. In addition, regarding the Rz of the exposed surface of the gas barrier layer (the exposed surface of the adhesion layer in the gas barrier film 6), the gas barrier films 3 to 12 according to the present invention showed a value of less than 35 nm.

<Performance evaluation of gas barrier film>
<Gas barrier properties (water vapor permeability)>
The gas barrier property was measured in accordance with the Mocon method (JIS K 7129-1992 B method), and was measured under the conditions of 38 ° C. and 100% RH using a water vapor permeability measuring device Aquatran manufactured by Mocon. And from the measurement result of the obtained water vapor permeability, ranking was performed according to the following criteria, and rank 3 or higher was regarded as acceptable. The evaluation results are shown in Table 2 below:
Rank 5: less than 1 × 10 ⁻² g / m ² · day Rank 4: 1 × 10 ⁻² g / m ² · day or more, less than 5 × 10 ⁻² g / m ² · day Rank 3: 5 × 10 ^{− 2} g / m ² · day or more, less than 1 × 10 ⁻¹ g / m ² · day Rank 2: 1 × 10 ⁻¹ g / m ² · day or more, less than 5 × 10 ⁻¹ g / m ² · day Rank 1: 5 × 10 ⁻¹ g / m ² · day or more.

<Humidity heat resistance>
After the gas barrier film sample was stored in an environment of 60 ° C. and 90% RH for 100 hours, the water vapor permeability after storage was measured by the same method as the “gas barrier property (water vapor permeability)” described above. Then, how many times the water vapor permeability after storage is increased compared to before storage is calculated as the degree of wet heat deterioration (= water vapor permeability after storage / water vapor permeability before storage), and according to the following criteria: Ranking was performed (rank 3 or higher was accepted). The evaluation results are shown in Table 2 below:
Rank 5: Degree of wet heat degradation is less than 2 times Rank 4: Degree of wet heat degradation is 2 times or more and less than 5 times Rank 3: Degree of wet heat degradation is 5 times or more and less than 10 times Rank 2: Degree of wet heat degradation is 10 times or more, 50 Less than double Rank 1: Degree of wet heat degradation is 50 times or more.

<Process suitability (abrasion resistance)>
A cylindrical stainless steel member having a radius of 15 mm is prepared, the surface of the gas barrier film sample on which the gas barrier layer is formed is wound 180 degrees so as to be in contact with the cylindrical member, and a tension of 10 g is applied per 1 cm width of the gas barrier film to give a second speed. The rubbing treatment was performed at a speed of 2 cm. This rubbing process was repeated 10 times. Then, how many times the water vapor permeability after the rubbing treatment is increased as compared with that before the rubbing treatment is calculated as the scratch deterioration degree (= water vapor permeability after rubbing treatment / water vapor permeability before rubbing treatment), Ranking was performed according to the following criteria (rank 3 or higher was accepted). The evaluation results are shown in Table 2 below:
Rank 5: Scratch degradation degree is less than 2 times Rank 4: Scratch degradation degree is 2 times or more and less than 5 times Rank 3: Scratch degradation degree is 5 times or more and less than 10 times Rank 2: Scratch degradation degree is 10 times or more, 50 Less than double Rank 1: The degree of scratch deterioration is 50 times or more.

From the results shown in Table 2, it was shown that according to the present invention, a gas barrier film excellent in gas barrier properties and wet heat resistance and improved in process suitability and a method for producing the same can be provided. In addition, the gas barrier film 6 in which the adhesion layer was disposed on the surface of the gas barrier layer showed better process suitability as compared with the gas barrier film 5 in which the adhesion layer was not disposed.

On the other hand, the gas barrier film 1 having a small surface hardness (SH) on the surface of the gas barrier layer was inferior in all evaluation items. Here, the small surface hardness of the surface of the gas barrier layer mainly reflects that the surface hardness of the base layer is small. Thus, the surface hardness of the base layer is small (that is, the base layer is soft). It is presumed that the underlayer is damaged by the plasma when the film is formed and the gas barrier property is lowered.

In addition, the gas barrier film 2 having a small amount of carbon (C) contained in the gas barrier layer (small y value) showed a certain performance with respect to the initial gas barrier property and wet heat resistance, but the result is inferior in process suitability. became. This is thought to be due to a decrease in scratch resistance as a result of an increase in rigidity of the gas barrier layer due to a small amount of carbon (C).

Similarly, the gas barrier film 14 having a large surface roughness (Ra) on the gas barrier layer surface was inferior in all evaluation items. The large surface roughness (Ra) of the gas barrier layer surface also mainly reflects that the surface roughness of the underlayer is large (because it is formed by sputtering). Therefore, even if a gas barrier layer is formed thereon, it cannot be sufficiently bonded and followed as a film, and it is presumed that the gas barrier property is lowered.

Furthermore, the gas barrier film 13 having a thick gas barrier layer having a thickness of 100 nm showed a certain performance with respect to initial gas barrier properties and process suitability, but was inferior in wet heat resistance. This is presumably because the gas barrier layer having a large film thickness cannot follow the deformation of the resin base material during storage in a humid heat environment, and cracks occurred in the gas barrier layer.

This application is based on Japanese Patent Application No. 2015-242459 filed on December 11, 2015, the disclosure of which is incorporated by reference in its entirety.

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

Claims (10)

A gas barrier film in which an underlayer and a gas barrier layer adjacent to each other are arranged in this order on at least one surface of a resin base material,
When the average composition of the gas barrier layer is expressed by SiO _x C _y (x and y are stoichiometric coefficients), y satisfies 0.40 <y ≦ 0.95,
The gas barrier layer has a thickness of 5 to 90 nm;
The surface hardness (SH) on the film surface on the side where the gas barrier layer is arranged with respect to the underlayer, measured by a nanoindentation method, is 1.4 to 3.5 GPa,
A gas barrier film having a surface roughness (Ra) of 1 to 18 nm on the film surface on the side where the gas barrier layer is disposed with respect to the underlayer. 2. The gas barrier film according to claim 1, wherein the underlayer contains Si and a metal M other than Si, and the M / Si ratio (molar ratio) is in the range of 0.001 to 0.05. The gas barrier film according to claim 1 or 2, wherein the gas barrier layer has a thickness of 10 to 60 nm. When the average composition of the underlayer is expressed by SiO _v C _w (v and w are stoichiometric coefficients), v satisfies 1.7 ≦ v ≦ 2.5, and w is 0.01 ≦ w ≦ 0. The gas barrier film according to any one of claims 1 to 3, which satisfies. The gas barrier film according to any one of claims 1 to 4, 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 5, wherein the adhesion layer has a thickness of 5 nm or less. Forming a coating film containing polysilazane on the resin base material, and applying a modification treatment to the coating film to form a base layer;
Forming a gas barrier layer using a vapor deposition method so as to be in contact with the underlayer;
A method for producing a gas barrier film comprising
When the average composition of the gas barrier layer is expressed by SiO _x C _y (x and y are stoichiometric coefficients), y satisfies 0.40 <y ≦ 0.95,
A method for producing a gas barrier film, wherein the gas barrier layer has a thickness of 5 to 90 nm. The method for producing a gas barrier film according to claim 7, further comprising a step of forming an adhesion layer containing an organosilicon compound having a polymerizable group on the gas barrier layer after the step of forming the gas barrier layer. The process for producing a gas barrier film according to claim 8, further comprising a step of subjecting the exposed surface of the gas barrier layer to a surface treatment after the step of forming the gas barrier layer and before the step of forming the adhesion layer. Method. The method for producing a gas barrier film according to claim 9, wherein the surface treatment is performed using an apparatus used for forming the gas barrier layer.

Images