JP6998734B2 - Laminates and devices containing them - Google Patents

Description

The present invention relates to a laminate, specifically a laminate containing a gas barrier film and an adhesive layer used in a device.

Conventionally, a gas barrier pressure-sensitive adhesive sheet having a gas barrier layer and a pressure-sensitive adhesive layer has been proposed (Patent Document 1). Further, a method for manufacturing a laminated body having a laminated film and an adhesive layer formed on one side of the laminated film is known (Patent Document 2).

WO2013 / 018602 JP-A-2016-78237

A laminate including a laminated film in which a gas barrier film and an adhesive layer are formed may have a peelable film on the adhesive layer on both surfaces for the purpose of surface protection or the like. In the bonding step with the device, the laminate is peeled off from the releaseable film and bonded to the device via the exposed pressure-sensitive adhesive layer. However, when the peelable film is peeled off, the peelable film on the side opposite to the adhesive layer side may be peeled off, bubbles may be generated, or the gas barrier film may be broken, resulting in device failure. be.

In order to solve the above problems, the present inventors have conducted detailed studies on a laminate having a gas barrier film, and have completed the present invention.

That is, the present invention includes the following preferred embodiments.
[1] A gas barrier film, a pressure-sensitive adhesive layer on one surface of the gas barrier film, a release film 1 on the other surface of the gas barrier film, and a side opposite to the gas barrier film side of the pressure-sensitive adhesive layer. It is a laminated body having a peelable film 2 on the surface, and is
The gas barrier film has a base material layer containing at least a flexible base material and an inorganic thin film layer on one surface of the base material layer.
Equation (1):
F1 ≧ F2 (1)
(In the formula (1), F1 represents the peel strength between the peelable film 1 and the gas barrier film, and F2 represents the peel strength between the peelable film 2 and the pressure-sensitive adhesive layer).
And equation (2):
G1 / G2 ≧ 0.4 (2)
(In the formula (2), G1 represents the rigidity of the peelable film 1 and G2 represents the rigidity of the peelable film 2).
A laminate that meets the requirements.
[2] The laminate according to [1], wherein F1 is 0.1 N / cm or more in the formula (1).
[3] The laminate according to [1] or [2], wherein the inorganic thin film layer contains a silicon atom, an oxygen atom and a carbon atom.
[4] The laminate according to any one of [1] to [3], wherein the base material layer has an organic layer A on at least one surface of a flexible base material.
[5] The method according to [3] or [4], wherein the atomic number ratio of carbon atoms to the total number of silicon atoms, oxygen atoms and carbon atoms contained in the inorganic thin film layer changes continuously in the thickness direction. Laminate.
[6] In the inorganic thin film layer, the average atomic number ratio of carbon atoms (C) to silicon atoms (Si) in the inorganic thin film layer is the formula (4) :.
0.10 <C / Si <0.50 (4)
The laminate according to any one of [3] to [5], which is in the range of.
[7] The ratio of the atomic number of silicon to the distance from the surface of the inorganic thin film layer in the film thickness direction of the inorganic thin film layer and the total number of silicon atoms, oxygen atoms and carbon atoms contained in the inorganic thin film layer. Conditions (i) and (ii): in the silicon distribution curve, the oxygen distribution curve, and the carbon distribution curve, which show the relationship between the atomic number ratio of oxygen and the atomic number ratio of carbon, respectively.
(I) The condition represented by the formula (8) is satisfied in the region where the atomic number ratio of silicon, the atomic number ratio of oxygen and the atomic number ratio of carbon are 90% or more in the film thickness direction of the inorganic thin film layer.
Atomic number ratio of oxygen> Atomic number ratio of silicon> Atomic number ratio of carbon (8)
(Ii) The laminate according to any one of [3] to [6], wherein the carbon distribution curve satisfies that the carbon distribution curve has at least one extremum.
[8] A device including the laminate according to any one of [1] to [7].

It is possible to improve the yield in the bonding process between the display device and the laminate having the gas barrier film.

The schematic sectional view of one form of the laminated body of this invention is shown. It is a schematic diagram which shows the manufacturing apparatus for manufacturing the gas barrier film in an Example. It is a graph which shows the XPS depth profile measurement result of the inorganic thin film layer in the gas barrier film obtained in Production Example 1. FIG.

The laminate of the present invention has a gas barrier film, a pressure-sensitive adhesive layer on one surface of the gas barrier film, a release film 1 on the other surface of the gas barrier film, and a gas barrier film side of the pressure-sensitive adhesive layer. The gas barrier film has a peelable film 2 on the surface opposite to the surface of the film, and the gas barrier film has a substrate layer containing at least a flexible substrate and an inorganic thin film layer on one surface of the substrate layer. The body.

(Gas barrier film)
The gas barrier film has a base material layer containing at least a flexible base material and an inorganic thin film layer on one surface of the base material layer. The inorganic thin film layer may be arranged on either the peelable film 1 side or the peelable film 2 side with respect to the flexible substrate, but it is better to arrange it on the peelable film 2 side for sealing performance. It is preferable from the viewpoint of.

(Base layer)
The base material layer may be one containing at least a flexible base material.

(Flexible base material)
As the flexible base material, a resin film containing at least one kind of resin as a resin component can be used, and a colorless and transparent resin film is preferable. Examples of the resin that can be used for the resin film include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyolefin resins such as polyethylene (PE), polypropylene (PP), and cyclic polyolefins; polyamide resins; polycarbonate resins; Polystyrene resin; polyvinyl alcohol resin; saponified product of ethylene-vinyl acetate copolymer; polyacrylonitrile resin; acetal resin; polyimide resin; polyether sulfide (PES) can be mentioned, and two or more of them can be combined as necessary. It can also be used. Among these, it is preferable to select and use from polyester resin and polyolefin resin according to necessary properties such as transparency, heat resistance and linear expandability, and it is more preferable to use PET, PEN and cyclic polyolefin. ..

The flexible base material may be an unstretched resin film, and the unstretched resin base material may be uniaxially stretched, tenter-type sequential biaxially stretched, tenter-type simultaneous biaxially stretched, tubular type simultaneous biaxially stretched, or the like. The resin film may be stretched in the flow direction (MD direction) of the resin base material and / or in the direction perpendicular to the flow direction of the resin base material (TD direction) by the known method.

The thickness of the flexible base material can be appropriately set in consideration of the production of a stable laminate. For example, from the viewpoint that the film can be conveyed even in a vacuum, it is preferably 5 to 500 μm, more preferably 10 to 200 μm, and even more preferably 50 to 100 μm.

The layer constituting the flexible substrate may be a retardation film having different refractive indexes of two orthogonal components in the plane, such as a λ / 4 retardation film and a λ / 2 retardation film. As the material of the retardation film, the orientation and solidification of cellulose-based resin, polycarbonate-based resin, polyarylate-based resin, polyester-based resin, acrylic resin, polysulfone-based resin, polyether sulfone-based resin, cyclic olefin-based resin, and liquid crystal compound. An example can be a layer or the like. Among them, a polycarbonate-based resin film is preferably used because a uniform film can be obtained at a low cost. As the film forming method, a solvent casting method or a precision extrusion method capable of reducing the residual stress of the film can be used, but the solvent casting method is preferably used from the viewpoint of uniformity. The stretching method is not particularly limited, and vertical uniaxial stretching between rolls, tenter horizontal uniaxial stretching, etc., which can obtain uniform optical characteristics, can be applied.

When the layer constituting the flexible substrate is a λ / 4 retardation film, the in-plane retardation Re (550) at a wavelength of 550 nm can be 100 to 180 nm, preferably 110 to 170 nm. , More preferably 120 to 160 nm.

When the layer constituting the flexible substrate is a λ / 2 retardation film, the in-plane retardation Re (550) at a wavelength of 550 nm can be 220 to 320 nm, preferably 240 to 300 nm. , More preferably 250 to 280 nm.

When the flexible substrate is a retardation film, the retardation value may exhibit a reverse wavelength dispersibility that increases with the wavelength of the measurement light, and the retardation value decreases with the wavelength of the measurement light. It may show a positive wavelength dispersion characteristic, or may show a flat wavelength dispersion characteristic in which the phase difference value hardly changes depending on the wavelength of the measured light.

When the flexible base material is a retardation film exhibiting reverse wavelength dispersibility, the flexible base material 10 is described as Re (λ) when the phase difference of the flexible base material at the wavelength λ is expressed as Re (λ). Re (450) / Re (550) <1 and Re (650) / Re (550)> 1 can be satisfied.

The flexible substrate is preferably colorless and transparent from the viewpoint of being able to transmit and absorb light. More specifically, the total light transmittance is preferably 80% or more, and more preferably 85% or more. Further, the haze value is preferably 5% or less, more preferably 3% or less, and further preferably 1% or less.

The flexible substrate is preferably insulating and preferably has an electrical resistivity of ¹⁰⁶ Ωcm or more from the viewpoint that it can be used as a substrate for organic or energy devices.

(Organic layer A)
The substrate layer may contain the same or different types of organic layer A on at least one surface of the flexible substrate for the purpose of improving adhesion and / or flatness to the inorganic thin film layer. .. Examples of the organic layer A include a flattening layer, a slippery layer and an anti-blocking layer.

When the base material layer contains the organic layer A, the base material layer may have an organic layer on only one surface of the flexible base material, or may have different types on both surfaces of the flexible base material. Those having an organic layer, for example, those having a flat layer on one surface and an easy-slip layer on the other surface may be used.

The organic layer A is usually coated with a resin composition containing a monomer and / or an oligomer of a photocurable resin such as an ultraviolet or electron beam curable resin on a flexible substrate, dried if necessary, and then dried. It can be formed by curing by irradiation with ultraviolet rays or electron beams. The resin composition may contain additives such as a solvent, a photopolymerization initiator, a thermal polymerization initiator, an antioxidant, an ultraviolet absorber, and a plasticizer, if necessary.

Examples of coating methods include various conventionally used coating methods such as spray coating, spin coating, bar coating, curtain coating, dipping method, air knife method, slide coating, hopper coating, reverse roll coating, and gravure coating. Examples include methods such as extraction application.

For the flattening layer, for example, an acrylate resin can be used. The acrylate resin is preferably a photocurable resin. The photocurable resin is a resin in which polymerization is started by ultraviolet rays, electron beams, or the like, and curing proceeds. Further, a resin other than the acrylate resin may be contained to the extent that the effect is not impaired. Specific examples thereof include polyester resin, isocyanate resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, phenol resin, urea melamine resin, styrene resin, alkyl titanate and the like, and one or more of these are included together. But it may be. Further, by changing the drying conditions and the curing conditions of the flattening layer, the flatness of the surface can be improved and the flattening layer can be used as an easy-slip layer or an anti-blocking layer.

As the flattening layer, when the temperature change of the elastic modulus of the flattening layer surface is evaluated by a rigid pendulum type physical property tester (for example, RPT-3000W manufactured by A & D Co., Ltd.), the flattening layer surface. It is preferable that the temperature at which the elastic modulus of the pendulum decreases by 50% or more is 150 ° C. or higher.

For the slippery layer, for example, a resin composition containing inorganic particles can be used. Examples of the inorganic particles include silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, zirconium oxide and the like. When the organic layer A is a slippery layer, the laminated body can be easily transported by roll.

For the anti-blocking layer, for example, a resin composition containing inorganic particles can be used. Examples of the inorganic particles include silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, zirconium oxide and the like. When the organic layer A is an anti-blocking layer, it is possible to easily prevent adhesion (blocking) due to contact between the laminated bodies.

(Inorganic thin film layer)
As the inorganic thin film layer, a layer of a known inorganic material having a gas barrier property can be appropriately used. Examples of inorganic materials are metal oxides, metal nitrides, metal oxynitrides, metal oxycarbides, and mixtures containing at least two of these. Further, as the inorganic material layer, a multilayer film in which two or more layers of the above-mentioned inorganic thin film layers are laminated can also be used. Further, the step of forming the inorganic thin film layer may be performed once or may be performed a plurality of times. When it is performed a plurality of times, it may be performed under the same conditions or under different conditions. Further, the inorganic thin film layer can be provided on one or both surfaces of the base material layer.

Above all, the inorganic thin film layer has at least silicon atoms (Si) and oxygen atoms (O) from the viewpoint of exhibiting higher water vapor permeation prevention performance, bending resistance, ease of manufacturing, and low manufacturing cost. , And preferably contains a carbon atom (C).

In this case, the inorganic thin film layer may be mainly composed of a compound represented by the general formula SiO _α C _β [in the formula, α and β represent positive numbers less than 2 independently of each other]. .. Here, "the main component" means that the content of the component is 50% by mass or more, preferably 70% by mass or more, and more preferably 90% by mass or more with respect to the mass of all the components constituting the inorganic thin film layer. It means that it is. The inorganic thin film layer may contain one kind of compound represented by the general formula SiO _α C _β , or may contain two or more kinds of compounds represented by the general formula SiO _α C _β . One or more of α and β in the above general formula may be a constant value or may change in the thickness direction of the inorganic thin film layer.

Further, the inorganic thin film layer contains elements other than silicon atom, oxygen atom and carbon atom, for example, one or more atoms of hydrogen atom, nitrogen atom, boron atom, aluminum atom, phosphorus atom, sulfur atom, fluorine atom and chlorine atom. It may be contained.

When the average atomic number ratio of carbon atoms (C) to silicon atoms (Si) in the inorganic thin film layer is expressed by C / Si, the inorganic thin film layer has high density and defects such as fine voids and cracks. From the viewpoint of reducing the amount of C / Si, it is preferable that the range of C / Si satisfies the formula (4).
0.10 <C / Si <0.50 (4)
Further, it is more preferably in the range of 0.15 <C / Si <0.45, further preferably in the range of 0.20 <C / Si <0.40, and 0.25 <C / Si <0. It is particularly preferable to be in the range of 35.

Further, the inorganic thin film layer has high denseness when the average atomic number ratio of oxygen atoms (O) to silicon atoms (Si) in the inorganic thin film layer is expressed by O / Si, and fine voids, cracks, etc. From the viewpoint of reducing the number of defects, it is preferably in the range of 1.50 <O / Si <1.90, more preferably in the range of 1.55 <O / Si <1.85, and 1.60 <O. The range of /Si <1.80 is more preferable, and the range of 1.65 <O / Si <1.75 is particularly preferable.

The average atomic number ratios C / Si and O / Si were measured in XPS depth profile under the following conditions, and from the obtained distribution curves of silicon atoms, oxygen atoms, and carbon atoms, the averages in the thickness direction of each atom were obtained. After determining the atomic concentration, the average atomic number ratios C / Si and O / Si can be calculated.
<XPS depth profile measurement>
Etching ion species: Argon (Ar ⁺ )
Etching rate (SiO ₂ thermal oxide film equivalent value): 0.027 nm / sec
Spatter time: 0.5 min
X-ray photoelectron spectrometer: ULVAC-PHI, model name "Quantara SXM"
Irradiated X-rays: Single crystal spectroscopy AlKα (1486.6 eV)
X-ray spot and its size: 100 μm
Detector: Pass Energy 69eV, Step size 0.125eV
Charge correction: Neutralizing electron gun (1eV), low-speed Ar ion gun (10V)

The inorganic thin film layer has a peak intensity (I ₁ ) existing at 950 to 1050 cm ^-1 and a peak existing at 1240 to 1290 cm ^-1 when infrared spectroscopic measurement (ATR method) is performed on the surface of the inorganic thin film layer. The strength ratio with the strength (I ₂ ) may be in the range satisfying the formula (5).
0.01 ≤ I ₂ / I ₁ <0.05 (5)

The peak intensity ratio I ₂ / I ₁ calculated from infrared spectroscopy (ATR method) is considered to represent the relative ratio of Si—CH ₃ to Si—O—Si in the inorganic thin film layer. It is considered that the inorganic thin film layer satisfying the relationship represented by the formula (5) has high denseness and few defects such as fine voids and cracks, so that it has excellent gas barrier properties and impact resistance. Be done. Regarding the range of the peak intensity ratio I ₂ / I ₁ , the range of 0.02 ≦ I ₂ / I ₁ <0.04 is preferable from the viewpoint of maintaining high denseness of the inorganic thin film layer.

Further, when the above-mentioned peak intensity ratio I ₂ / I ₁ is satisfied, the gas barrier film becomes moderately slippery and more difficult to block. On the contrary, when I ₂ / I ₁ is large, that is, when Si—C is too large, the flexibility is poor and the slipperiness tends to be difficult. Also, even if I ₂ / I ₁ is small, that is, Si—C is too small, the flexibility tends to decrease.

Infrared spectroscopy of the surface of the inorganic thin film layer is performed by a Fourier transform infrared spectrophotometer (FT / IR-460Plus, manufactured by Nippon Spectroscopy Co., Ltd.) equipped with an ATR attachment (PIKE MIRacle) using a germanium crystal for the prism. Can be measured by.

The inorganic thin film layer has a peak intensity (I ₁ ) existing at 950 to 1050 cm ^-1 and a peak existing at 770 to 830 cm ^-1 when infrared spectroscopic measurement (ATR method) is performed on the surface of the inorganic thin film layer. The strength ratio with the strength (I ₃ ) may be in the range of the formula (6).
0.25 ≤ I ₃ / I ₁ ≤ 0.50 (6)

The peak intensity ratio I ₃ / I ₁ calculated from infrared spectroscopy (ATR method) is considered to represent the relative ratio of Si—C, Si—O, etc. to Si—O—Si in the inorganic thin film layer. .. It is considered that the inorganic thin film layer satisfying the relationship represented by the formula (6) has excellent bending resistance and impact resistance because carbon is introduced while maintaining high denseness. Regarding the range of the peak intensity ratio I ₃ / I ₁ , the range of 0.25 ≤ I ₃ / I ₁ ≤ 0.50 is preferable, and 0.30, from the viewpoint of maintaining the balance between the compactness and the bending resistance of the inorganic thin film layer. The range of ≦ I ₃ / I ₁ ≦ 0.45 is more preferable.

The thin film layer has a peak intensity (I ₃ ) existing at 770 to 830 cm ^-1 and a peak existing at 870 to 910 cm ^-1 when infrared spectroscopic measurement (ATR method) is performed on the surface of the inorganic thin film layer. The strength ratio with the strength (I ₄ ) may be in the range of the formula (7).
0.70 ≤ I ₄ / I ₃ <1.00 (7)

The peak intensity ratio I ₄ / I ₃ calculated from infrared spectroscopy (ATR method) is considered to represent the ratio of peaks related to Si—C in the inorganic thin film layer. It is considered that the inorganic thin film layer satisfying the relationship represented by the formula (7) has excellent bending resistance and impact resistance because carbon is introduced while maintaining high denseness. Regarding the range of the peak intensity ratio I ₄ / I ₃ , the range of 0.70 ≦ I ₄ / I ₃ <1.00 is preferable, and 0.80 from the viewpoint of maintaining the balance between the compactness and the bending resistance of the inorganic thin film layer. The range of ≦ I ₄ / I ₃ <0.95 is more preferable.

The thickness of the inorganic thin film layer is preferably 5 to 3000 nm from the viewpoint of making it difficult to crack when the inorganic thin film layer is bent. Further, when the inorganic thin film layer is formed by the plasma CVD method using glow discharge plasma, the inorganic thin film layer is formed while being discharged through the substrate, so that the thickness is more preferably 10 to 2000 nm. It is more preferably ~ 1000 nm.

The average density of the inorganic thin film layer may be 1.8 g / cm ³ or more. The "average density" of the inorganic thin film layer is the number of silicon atoms, the number of carbon atoms and the number of oxygen atoms obtained by the Rutherford Backscattering Spectrometery (RBS), and the hydrogen forward scattering method (Hydrogen Forward scattering). Calculate the weight of the inorganic thin film layer in the measurement range from the number of atoms of hydrogen obtained by (Scatterery: HFS), and divide by the volume of the inorganic thin film layer in the measurement range (product of ion beam irradiation area and film thickness). It is required by that. Since the average density of the inorganic thin film layer is 1.8 g / cm ³ or more, the inorganic thin film layer has a structure having high density and few defects such as fine voids and cracks. Further, when the inorganic thin film layer is composed of a silicon atom, an oxygen atom, a carbon atom and a hydrogen atom, the average density of the inorganic thin film layer is preferably less than 2.22 g / cm ³ .

A curve showing the relationship between the distance from the surface of the inorganic thin film layer in the film thickness direction of the inorganic thin film layer and the atomic number ratio of silicon atoms at each distance is called a silicon distribution curve. Similarly, a curve showing the relationship between the distance from the surface of the inorganic thin film layer in the film thickness direction and the atomic number ratio of oxygen atoms at each distance is called an oxygen distribution curve. Further, a curve showing the relationship between the distance from the surface of the inorganic thin film layer in the film thickness direction and the atomic number ratio of carbon atoms at each distance is called a carbon distribution curve. Here, the atomic number ratio of silicon atoms, the atomic number ratio of oxygen atoms, and the atomic number ratio of carbon atoms are from the surface of the inorganic thin film layer to the total number of silicon atoms, oxygen atoms, and carbon atoms contained in the inorganic thin film layer. It means the ratio of the number of atoms at each distance.

From the viewpoint of easily suppressing the deterioration of gas barrier properties due to bending, the atomic number ratio of carbon atoms to the total number of silicon atoms, oxygen atoms and carbon atoms contained in the inorganic thin film layer is continuous in the thickness direction of the inorganic thin film layer. It is preferable to change to. Here, the fact that the atomic number ratio of carbon atoms changes continuously in the thickness direction means that, for example, in the carbon distribution curve described above, the atomic number ratio of carbon atoms has a plurality of extreme values within a predetermined displacement width. It means that the increase and decrease are continuously repeated, and that the part that changes discontinuously is not included, that is, the atomic number ratio of carbon atoms does not increase or decrease monotonically. As an example in which the atomic number ratio continuously changes in the thickness direction, a graph (FIG. 3) showing the XPS depth profile measurement result of the inorganic thin film layer in the gas barrier film obtained in Production Example 1 described later is referred to.

It is preferable that the atomic number ratio and the carbon distribution curve obtained from the silicon distribution curve, the oxygen distribution curve and the carbon distribution curve in the inorganic thin film layer satisfy the conditions (i) and (ii) from the viewpoint of gas barrier property and flexibility. ..
(I) The condition represented by the formula (8) is satisfied in the region where the atomic number ratio of silicon, the atomic number ratio of oxygen and the atomic number ratio of carbon are 90% or more in the film thickness direction of the inorganic thin film layer.
(Atom ratio of oxygen)> (Atom ratio of silicon)> (Atom ratio of carbon) (8) (ii) The carbon distribution curve has at least one extreme value.

The carbon distribution curve of the inorganic thin film layer is preferably substantially continuous. The fact that the carbon distribution curve is substantially continuous means that the carbon distribution curve does not include a portion where the atomic number ratio of carbon changes discontinuously. Specifically, it is preferable to satisfy the formula (9) when the distance from the surface of the thin film layer in the film thickness direction is x [nm] and the atomic number ratio of carbon is C.
| DC / dx | ≤0.01 (9)

Further, the carbon distribution curve of the inorganic thin film layer preferably has at least one extremum. The extreme value here is a maximum value or a minimum value of the atomic number ratio of each element with respect to the distance from the surface of the inorganic thin film layer in the film thickness direction. The extreme value is at the point where the atomic number ratio of the element changes from increasing to decreasing or the atomic number ratio of the element changes from decreasing to increasing when the distance from the surface of the inorganic thin film layer in the film thickness direction is changed. It is the value of the atomic number ratio of. The extreme value can be obtained, for example, based on the measured atomic number ratio at a plurality of measurement positions in the film thickness direction. The measurement position of the atomic number ratio is set so that the interval in the film thickness direction is, for example, 20 nm or less. For the positions showing extreme values in the film thickness direction, for discrete data groups including the measurement results at each measurement position, for example, the measurement results at three or more different measurement positions are compared, and the measurement results increase or decrease. It can be obtained by finding the position where it turns to or the position where it turns from decrease to increase. The position showing the extremum can also be obtained, for example, by differentiating the approximate curve obtained from the above-mentioned discrete data group. When the section where the atomic number ratio increases or decreases monotonically from the position showing the extreme value is, for example, 20 nm or more, the atomic number ratio at the position moved by 20 nm in the film thickness direction from the position showing the extreme value and the pole. The absolute value of the difference from the value is, for example, 0.03 or more.

In the inorganic thin film layer formed so as to satisfy the condition that the carbon distribution curve has at least one extremum as described above, the amount of increase in the gas permeability after bending with respect to the gas permeability before bending determines the above conditions. It will be less than when it is not satisfied. That is, by satisfying the above conditions, the effect of suppressing the deterioration of the gas barrier property due to bending can be obtained. When the inorganic thin film layer is formed so that the number of extreme values of the carbon distribution curve is two or more, the amount of increase is smaller than that of the case where the number of extreme values of the carbon distribution curve is one. .. Further, when the inorganic thin film layer is formed so that the number of extreme values of the carbon distribution curve is three or more, the amount of increase is larger than that of the case where the number of extreme values of the carbon distribution curve is two. Less. When the carbon distribution curve has two or more extrema, the distance from the surface of the inorganic thin film layer in the film thickness direction at the position showing the first extremum and the second extremum adjacent to the first extremum. The absolute value of the difference from the distance from the surface of the inorganic thin film layer in the film thickness direction at the position indicating the value is preferably in the range of 1 nm or more and 200 nm or less, and further preferably in the range of 1 nm or more and 100 nm or less. preferable.

Further, it is preferable that the absolute value of the difference between the maximum value and the minimum value of the atomic number ratio of carbon in the carbon distribution curve of the inorganic thin film layer is 0.01 or more. In the inorganic thin film layer formed so as to satisfy the above conditions, the amount of increase in the gas permeability after bending with respect to the gas permeability before bending is smaller than that in the case where the conditions are not satisfied. That is, by satisfying the above conditions, the effect of suppressing the deterioration of the gas barrier property due to bending can be obtained. When the absolute value of the difference between the maximum value and the minimum value of the atomic number ratio of carbon is 0.02 or more, the above effect is high, and when it is 0.03 or more, the above effect is further high.

The lower the absolute value of the difference between the maximum value and the minimum value of the atomic number ratio of silicon in the silicon distribution curve, the better the gas barrier property of the inorganic thin film layer tends to be. From this point of view, the absolute value is preferably less than 0.05 (less than 5 at%), more preferably less than 0.04 (less than 4 at%), and less than 0.03 (3 at%). Less than) is particularly preferred.

Further, in the oxygen carbon distribution curve, the difference between the maximum value and the minimum value of the total atomic number ratio is defined as the "total atomic number ratio" when the total of the atomic number ratio of oxygen atoms and the atomic number ratio of carbon atoms at each distance is taken as "total atomic number ratio". The lower the absolute value of, the better the gas barrier property of the inorganic thin film layer tends to be. From this point of view, the total atomic number ratio is preferably less than 0.05, more preferably less than 0.04, and particularly preferably less than 0.03.

When the inorganic thin film layer has a substantially uniform composition in the surface direction of the inorganic thin film layer, the gas barrier property of the inorganic thin film layer can be made uniform and improved. The substantially uniform composition means the number of extreme values existing in the film thickness direction at any two points on the surface of the inorganic thin film layer in the oxygen distribution curve, the carbon distribution curve, and the oxygen carbon distribution curve. Is the same, and the absolute value of the difference between the maximum value and the minimum value of the carbon atom number ratio in each carbon distribution curve is the same as each other or the difference is within 0.05.

The inorganic thin film layer formed so as to satisfy the above conditions can exhibit the gas barrier property required for, for example, a flexible electronic device using an organic EL element.

Such an inorganic thin film layer containing silicon atoms, oxygen atoms and carbon atoms is preferably formed by a chemical vapor deposition method (CVD method), and above all, a plasma chemical vapor deposition method using glow discharge plasma or the like. It is more preferably formed by (PECVD method).

Examples of the raw material gas include an organosilicon compound containing a silicon atom and a carbon atom. Examples of organic silicon compounds include hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, and propyl. Examples thereof include silane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane and octamethylcyclotetrasiloxane. Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoint of the handleability of the compound and the gas barrier property of the obtained inorganic thin film layer. In addition, these organosilicon compounds can be used alone or in combination of two or more.

Further, a reaction gas capable of reacting with the raw material gas to form an inorganic compound such as an oxide or a nitride can be appropriately selected and mixed with the raw material gas. As the reaction gas for forming the oxide, for example, oxygen or ozone can be used. Further, as the reaction gas for forming the nitride, for example, nitrogen or ammonia can be used. These reaction gases can be used alone or in combination of two or more. For example, in the case of forming an oxynitride, the reaction gas for forming an oxide and the nitride are formed. Can be used in combination with a reaction gas for. The flow rate ratio of the raw material gas and the reaction gas can be appropriately adjusted according to the atomic number ratio of the inorganic material to be formed.

The C / Si value can be controlled by adjusting the flow rate ratio of the raw material gas and the reaction gas. For example, when hexamethyldisiloxane (HMDSO) is used as the raw material gas and oxygen is used as the reaction gas, the ratio of oxygen flow rate to HMDSO flow rate O ₂ / HMDSO is set to the range of 5 to 25, and the C / Si value is set. It can be controlled within the above range.

If necessary, a carrier gas may be used to supply the raw material gas into the vacuum chamber. Further, in order to generate plasma discharge, a discharge gas may be used, if necessary. As such a carrier gas and a gas for discharge, known ones can be used as appropriate, and for example, a rare gas such as helium, argon, neon, or xenon; hydrogen can be used.

The pressure (degree of vacuum) in the vacuum chamber can be appropriately adjusted according to the type of raw material gas and the like, but is preferably in the range of 0.5 to 50 Pa.

FIG. 2 is a schematic diagram showing an example of a manufacturing apparatus used for manufacturing an inorganic thin film layer contained in a gas barrier film, and is a schematic diagram of an apparatus for forming an inorganic thin film layer by a plasma chemical vapor deposition method. In FIG. 2, the dimensions and ratios of the components are appropriately different in order to make the drawings easier to see. The manufacturing apparatus shown in FIG. 2 is a magnetic field forming apparatus installed inside the delivery roll 11, the take-up roll 71, the transfer rolls 21 to 24, the gas supply pipe 41, the plasma generation power supply 51, and the film forming rolls 31 and 32, respectively. It has 61 and 62. In the apparatus of FIG. 2, the film forming rolls 31 and 32 also serve as electrodes, and are roll-shaped electrodes described later.

Among the components of the manufacturing apparatus, at least the film forming roll, the gas supply pipe, and the magnetic field forming apparatus are arranged in a vacuum chamber (not shown) when forming the inorganic thin film layer. This vacuum chamber is connected to a vacuum pump (not shown). The pressure inside the vacuum chamber is adjusted by the operation of the vacuum pump.

By using this device, by controlling the power supply for plasma generation, it is possible to generate the discharge plasma of the film-forming gas supplied from the gas supply pipe in the space between the two film-forming rolls, and the generated discharge. Plasma CVD film formation can be performed by a continuous film formation process using plasma.

The film 100 before film formation is installed on the delivery roll in a wound state, and the film is fed while being unwound in the long direction. Further, a take-up roll is provided on the end side of the film, and after the film is formed, the film is taken up while being towed and stored in a roll shape.

It is preferable that the two film forming rolls extend in parallel and are arranged to face each other. Both rolls are made of a conductive material and carry the film while rotating. It is preferable to use two film forming rolls having the same diameter, and for example, it is preferable to use one having a diameter of 5 cm or more and 100 cm or less.

When the inorganic thin film layer is formed, the base material layer is conveyed to the surface of the pair of roll-shaped electrodes while being in close contact with each other, plasma is generated between the pair of electrodes, and the raw material is decomposed in the plasma to be flexible. It is preferable to form an inorganic thin film layer on the substrate. In the pair of electrodes, magnets are preferably arranged inside the electrodes so that the magnetic flux density is high on the surfaces of the electrodes and the flexible base material. As a result, the plasma tends to be constrained at high density on the electrodes and the flexible substrate when the plasma is generated.

(Organic layer B)
The gas barrier film may have an organic layer B in the outermost layer of the gas barrier film.
Examples of the organic layer B include an ultraviolet blocking layer, a matting agent layer, a protective layer, an anti-fog layer, a smoothing layer, an adhesion improving layer, a light-shielding layer, an anti-reflection layer, a hard coat layer, a stress relaxation layer, an anti-fog layer, and an anti-fouling layer. Examples thereof include a layer, a layer to be printed, and a hard coat layer such as an easy-adhesion layer. The organic layer B may be laminated on the surface of the inorganic thin film layer opposite to the base material layer, or may be laminated on the inorganic thin film layer, for example. From the viewpoint of water vapor barrier property, the gas barrier film of the present invention preferably further has an organic layer B on the surface of the inorganic thin film layer opposite to the base material layer.

Examples of the organic layer B include a layer composed of the resin described for the organic layer A and a layer containing an additive for exerting each function in the resin described for the organic layer A, and examples thereof include a gas barrier. It is appropriately selected depending on the intended use and usage of the sex film.

Examples of the method for laminating the organic layer B include the method described for the organic layer A above.

Further, the organic layer B may be a layer formed by using a composition containing an inorganic polymer such as polysilazane. By forming the inorganic polymer layer, the permeation of water vapor can be prevented at a high level, and when applied to an electronic device such as an organic EL element, the generation of dark spots can be suppressed for a long period of time. can.

The inorganic polymer layer can be adjusted to a desired film thickness by one coating, or can be applied multiple times to adjust to a desired film thickness. When the coating is applied a plurality of times, it is more effective to carry out the curing treatment for each coating from the viewpoint of securing the diffusion path of the gas generated by the curing and compensating for defects such as cracks.

The inorganic polymer layer can be formed by applying a coating liquid containing an inorganic polymer such as polysilazane on the inorganic thin film layer, drying the coating film, and then curing the formed coating film. As the coating liquid, one in which an inorganic polymer is dissolved or dispersed in a solvent can be used. The concentration of the inorganic polymer in the coating liquid may be appropriately adjusted according to the thickness of the inorganic polymer layer and the pot life of the coating liquid, but is usually 0.2 to 35% by mass.

More specific examples of polysilazane, which is an inorganic polymer, include perhydropolysilazane (PHPS).

As the solvent, a solvent that does not react with the inorganic polymer to be used, is suitable for dissolving or dispersing the inorganic polymer, and does not adversely affect the inorganic thin film layer can be appropriately selected and used. Examples of the solvent include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, and ethers such as halogenated hydrocarbon solvents, aliphatic ethers and alicyclic ethers. More specific examples of the solvent include hydrocarbons such as pentane, hexane, cyclohexane, toluene and xylene, halogenated hydrocarbons such as methylene chloride and trichloroethane, and ethers such as dibutyl ether, dioxane and tetrahydrofuran. Two or more kinds of these solvents may be mixed and used.

When polysilazane is used as the inorganic polymer, an amine catalyst, a Pt compound such as Pt acetylacetonate, a Pd compound such as propionic acid Pd, and a Rh compound such as Rh acetylacetonate are used in the coating liquid in order to promote the modification to silicon nitride. It is also possible to add a metal catalyst such as.

The amount of the catalyst added to polysilazane is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and 0.5 to 2% by mass based on the total amount of the coating liquid. Is even more preferable. By setting the amount of the catalyst added within the above range, it is possible to suppress excessive silanol formation, a decrease in film density, an increase in film defects, etc. due to the rapid progress of the reaction.

Drying may be performed under conditions where the solvent in the coating liquid can be removed. Further, for example, the coating liquid may be applied and dried at the same time on a heated hot plate.

Examples of the curing treatment method for the formed coating film include a plasma CVD method, an ion implantation treatment method, an ultraviolet irradiation method, a vacuum ultraviolet irradiation method, an oxygen plasma irradiation method, and a heat treatment method, in which an inorganic polymer in the coating film is cured. Any method that can be used can be used. Among these, as the curing treatment method, it is preferable to use a method of irradiating the coating film with vacuum ultraviolet light (VUV light) having a wavelength of 200 nm or less. Further, the method of irradiating the coating film with vacuum ultraviolet light is more preferable when polysilazane is used as the inorganic polymer.

When the vacuum ultraviolet irradiation method is used as the curing treatment method for the coating film containing polysilazane, when the coating film is irradiated with vacuum ultraviolet rays, at least a part of polysilazane is modified to silicon nitride represented by SiO _{x Ny} . To. Here, when perhydropolysilazane having a structure represented by-(SiH ₂ -NH-) _n- is used as polysilazane, oxygen is required for x> 0 when reforming to SiO _x N _y . A source is required, but oxygen and water taken into the coating film during the manufacturing process serve as the oxygen source.

In the composition of SiO _x N _y , x and y are basically in the range of 2x + 3y = 4 due to the relationship between the bonds of Si, O, and N. In the state of y = 0 where the oxidation is completely advanced, the silanol group is contained in the coating film, and the range may be in the range of 2 <x <2.5. Since it is usually unlikely that nitriding will proceed more than the oxidation of Si, y is basically 1 or less.

The reaction mechanism in which silicon nitride is generated from perhydropolysilazane and silicon oxide is generated by irradiation with vacuum ultraviolet rays is considered as follows.

(1) Dehydrogenation and accompanying formation of Si—N bonds The Si—H bonds and NH bonds in perhydropolysilazane are relatively easily cleaved by excitation by vacuum ultraviolet irradiation or the like, and Si under an inert atmosphere. It is considered to recombine as -N (unbonded hands of Si may be formed). That is, perhydropolysilazane cures as a _SiNy composition without oxidation. In this case, cleavage of the polymer backbone does not occur. Cleavage of Si—H bonds and NH bonds is promoted by the presence of a catalyst and heating. _The cleaved H is released to the outside of the membrane as H2.

(2) Formation of Si—O—Si bond by hydrolysis and dehydration condensation The Si—N bond in perhydropolysilazane is hydrolyzed by water, and the polymer main chain is cleaved to form Si—OH. The two Si—OH dehydrate and condense to form a Si—O—Si bond and cure. Although this is a reaction that occurs even in the atmosphere, it is considered that water vapor generated as outgas from the resin substrate due to the heat of irradiation is the main water source during the irradiation with vacuum ultraviolet rays in an inert atmosphere. When the water content becomes excessive, Si—OH that cannot be completely dehydrated and condensed remains, resulting in a cured film having a low gas barrier property represented by the compositions of SiO _2.1 to SiO _2.3 .

(3) Direct oxidation by singlet oxygen, formation of Si—O—Si bond When an appropriate amount of oxygen is present in the atmosphere during vacuum ultraviolet irradiation, singlet oxygen with extremely strong oxidizing power is formed. H and N in perhydropolysilazane replace O to form Si—O—Si bonds and cure. It is considered that the recombination of the bond may occur due to the cleavage of the polymer backbone.

(4) Oxidation accompanied by Si—N bond cleavage by vacuum ultraviolet irradiation and excitation Since the energy of vacuum ultraviolet is higher than the binding energy of Si—N in perhydropolysilazane, the Si—N bond is cleaved and oxygen is generated in the surroundings. In the presence of an oxygen source such as ozone or water, it is considered that it is oxidized to form a Si—O—Si bond or a Si—ON bond. It is considered that the recombination of the bond may occur due to the cleavage of the polymer backbone.

The composition of the silicon nitride in the layer obtained by irradiating the coating film containing polysilazane with vacuum ultraviolet rays is adjusted by appropriately combining the oxidation mechanisms of (1) to (4) described above to control the oxidation state. It can be carried out.

In the vacuum ultraviolet irradiation, the illuminance of the vacuum ultraviolet on the coating film surface received by the coating film containing polysilazane is preferably in the range of 1 to 100,000 mW / cm ² , and preferably in the range of 30 to 200 mW / cm ² . Is more preferable. If the illuminance is 1 mW / cm ² or more, there is no concern that the reforming efficiency will decrease, and if it is 100,000 mW / cm ² or less, the coating film will not be ablated and the flexible substrate will be damaged. It is preferable because it does not exist.

In vacuum ultraviolet irradiation, the integrated light amount (integrated irradiation energy amount) of the vacuum ultraviolet emitted to the coating film containing polysilazane is 1.0 to 100 mJ / in the following formula standardized by the film thickness of the inorganic polymer layer. It is preferably in the range of cm ² / nm, more preferably in the range of 1.5 to 30 mJ / cm ² / nm, and further preferably in the range of 2.0 to 20 mJ / cm ² / nm. It is preferably in the range of 5.0 to 20 mJ / cm ² / nm, particularly preferably. When the standardized integrated light amount is 1.0 mJ / cm ² / nm or more, the modification can be sufficiently performed. On the other hand, when the standardized integrated light amount is 100 mJ / cm ² / nm or less, the over-modification condition does not occur and the generation of cracks in the inorganic polymer layer can be prevented. Even when the inorganic polymer layer is cured a plurality of times in order to obtain a desired film thickness, it is preferable that the amount of light is within the standardized integrated light amount for each layer.

A noble gas excimer lamp is preferably used as the vacuum ultraviolet light source. Noble gas atoms such as Xe, Kr, Ar, and Ne are called inert gases because they do not chemically bond to form molecules.

However, the excited atoms of the noble gas that gained energy by electric discharge or the like can be combined with other atoms to form molecules. If the noble gas is xenon
e + Xe → Xe ^*
Xe ^* + 2Xe → Xe ₂ ^* + Xe
Xe ₂ ^* → Xe + Xe + hν (172nm)
Then, when the excited excimer molecule Xe ₂ ^* transitions to the ground state, it emits excimer light having a wavelength of 172 nm.

One of the characteristics of excimer lamps is that they are highly efficient because the radiation is concentrated on one wavelength and almost no light other than the required light is emitted. In addition, since extra light is not emitted, the temperature of the object can be kept low. Furthermore, since it does not take time to start and restart, it is possible to turn on and blink instantly.

A method using a dielectric barrier discharge is known to obtain excimer light. Dielectric barrier discharge occurs in the gas space by arranging a gas space between both electrodes via a dielectric such as transparent quartz and applying a high voltage of several tens of kHz to the electrodes, which is very similar to lightning. It is a discharge called a fine micro discharge, and when the streamer of the micro discharge reaches the tube wall (derivative), an electric charge is accumulated on the surface of the dielectric, so that the micro discharge disappears.

This micro discharge spreads over the entire tube wall and is a discharge that is repeatedly generated and extinguished. For this reason, light flicker that can be confirmed with the naked eye occurs. In addition, a streamer with a very high temperature reaches the pipe wall directly locally, which may accelerate the deterioration of the pipe wall.

As a method for efficiently obtaining excimer light emission, an electrodeless electric field discharge is also possible in addition to the dielectric barrier discharge. Electrodeless electric field discharge due to capacitive coupling, also known as RF discharge. The lamp, the electrodes, and their arrangement may be basically the same as the dielectric barrier discharge, but the high frequency applied between the two electrodes is lit at several MHz. Since the electrodeless electric field discharge can obtain a uniform discharge spatially and temporally in this way, a long-life lamp without flicker can be obtained.

In the case of dielectric barrier discharge, micro discharge occurs only between the electrodes, so the outer electrode covers the entire outer surface to allow discharge in the entire discharge space, and transmits light to extract light to the outside. Must be something to do.

Therefore, an electrode made of a thin metal wire in a mesh shape is used. Since this electrode uses as thin a wire as possible so as not to block light, it is easily damaged by ozone or the like generated by vacuum ultraviolet light in an oxygen atmosphere. In order to prevent this, it is necessary to create an atmosphere of an inert gas such as nitrogen around the lamp, that is, inside the irradiation device, and to provide a window of synthetic quartz to take out the irradiation light. Synthetic quartz windows are not only an expensive consumable, but also light loss.

Since the double cylindrical lamp has an outer diameter of about 25 mm, the difference in the distance to the irradiation surface cannot be ignored between the area directly under the lamp shaft and the side surface of the lamp, which causes a large difference in illuminance. Therefore, even if the lamps are arranged in close contact with each other, a uniform illuminance distribution cannot be obtained. If the irradiation device is provided with a synthetic quartz window, the distance in the oxygen atmosphere can be made uniform, and a uniform illuminance distribution can be obtained.

When electrodeless electric field discharge is used, it is not necessary to make the external electrodes into a mesh. Glow discharge spreads over the entire discharge space simply by providing an external electrode on a part of the outer surface of the lamp. As the external electrode, an electrode that also serves as a light reflector made of an aluminum block is usually used on the back of the lamp. However, since the outer diameter of the lamp is large as in the case of dielectric barrier discharge, synthetic quartz is required to obtain a uniform illuminance distribution.

The biggest feature of the thin tube excimer lamp is its simple structure. Both ends of the quartz tube are closed, and a gas for excimer emission is enclosed inside.

The outer diameter of the tube of the thin tube lamp is about 6 to 12 mm, and if it is too thick, a high voltage is required for starting.

As the discharge form, either a dielectric barrier discharge or an electrodeless electric field discharge can be used. The shape of the electrode may be a flat surface in contact with the lamp, but by making the shape match the curved surface of the lamp, the lamp can be firmly fixed, and the electrode is in close contact with the lamp, so that the discharge is more stable. .. Moreover, if the curved surface is made a mirror surface with aluminum, it can also be used as a light reflector.

The Xe excimer lamp has excellent luminous efficiency because it emits ultraviolet rays having a short wavelength of 172 nm at a single wavelength. Since this excimer light has a large oxygen absorption coefficient, it is possible to generate radical oxygen atom species and ozone at a high concentration with a small amount of oxygen.

It is also known that the energy of light having a short wavelength of 172 nm has a high ability to dissociate the bonds of organic substances. The high energy of active oxygen, ozone, and ultraviolet radiation can be used to modify the polysilazane layer in a short time.

Therefore, compared to low-pressure mercury lamps and plasma cleaning with wavelengths of 185 nm and 254 nm, it is possible to shorten the process time due to high throughput, reduce the equipment area, and irradiate organic materials and plastic substrates that are susceptible to heat damage. ..

Since excimer lamps have high light generation efficiency, they can be turned on with low power input. In addition, it does not emit light with a long wavelength that causes the temperature to rise due to light irradiation, and irradiates energy in the ultraviolet region, that is, in a short wavelength range, so it has the characteristic of suppressing the rise in the surface temperature of the object to be irradiated. .. Therefore, it is suitable for reforming a material having a flexible film such as PET, which is considered to be easily affected by heat.

Since vacuum ultraviolet rays are absorbed by oxygen in the presence of oxygen, the efficiency in the ultraviolet irradiation step tends to decrease. Therefore, it is preferable to perform vacuum ultraviolet irradiation in a state where the oxygen concentration is as low as possible. That is, the oxygen concentration during vacuum ultraviolet irradiation is preferably in the range of 10 to 100,000 volume ppm, more preferably in the range of 50 to 50,000 volume ppm, and further preferably in the range of 100 to 10,000 volume ppm. be.

When irradiating with vacuum ultraviolet rays, it is preferable to use a dry inert gas as the gas that satisfies the irradiation environment, and above all, it is preferable to use dry nitrogen gas from the viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rates of the oxygen gas and the inert gas introduced into the irradiation environment and changing the flow rate ratio.

(Standing coefficient of friction)
The gas barrier film has a coefficient of static friction between one surface of the gas barrier film and the other surface of 0.30 or more and 2.0 or less.

The coefficient of static friction is such that the gas barrier film having the upper surface and the lower surface is divided into two sheets, and the upper surface of the first gas barrier film and the lower surface of the second gas barrier film are brought into contact with each other. The coefficient may be measured. The coefficient of static friction conforms to the inclination method of JIS P 8147 and can be measured in an environment of a temperature of 23 ° C. and a humidity of 50 RH%.

To adjust the coefficient of static friction, the surface roughness of both sides of the gas barrier film may be adjusted. For example, when the inorganic thin film layer is provided on only one surface of the base material layer, the surface roughness of the exposed surface of the inorganic thin film layer and the surface roughness of the exposed surface of the base material layer may be adjusted. When the inorganic thin film layer is provided on both surfaces of the base material layer, the surface roughness of the exposed surface of one inorganic thin film layer and the surface roughness of the exposed surface of the other inorganic thin film layer may be adjusted. Increasing the surface roughness of at least one surface of the gas barrier film tends to reduce the coefficient of static friction between the front and back surfaces.

(Surface roughness)
The surface roughness of the inorganic thin film layer can be changed, for example, according to the conditions such as the pressure (vacuum degree) in the vacuum chamber and the film thickness in the film forming conditions of the inorganic thin film layer, and the composition of the inorganic thin film layer. Further, the surface roughness of the inorganic thin film layer adjusts the surface roughness of the underlying flexible base material and the surface roughness of the intermediate layer arranged between the inorganic thin film layer and the flexible base material. Can also be adjusted by.

In order to adjust the surface roughness of the flexible substrate, a treatment such as a corona treatment may be performed.

The arithmetic mean roughness Ra of the surface of the inorganic thin film layer can be 3 nm or less. The arithmetic mean roughness Ra can be obtained by attaching a gas barrier film to an epoxy plate with an adhesive and then observing the surface thereof with a white interference microscope. The arithmetic mean roughness Ra is the arithmetic mean roughness according to JIS B 0601: 2001.

(warp)
Further, in the gas barrier film according to the present embodiment, when a 50 mm square portion cut out from the gas barrier film is placed so that the central portion of the portion is in contact with the horizontal plane, the average distance from the horizontal plane to the four corners warped is average. The value is 2 mm or less.

This average value can be measured as follows. First, the gas barrier film is held at a temperature of 23 ° C. and a humidity of 50 RH% for 48 hours. Next, a 50 mm square portion is cut out from the gas barrier film to obtain a sample. The sample is placed on the horizontal plane so that the central portion of the sample is in contact with the horizontal plane, and a total of 4 points are obtained from the horizontal plane to the four corners. Finally, the average value of these four points is obtained.

In order to reduce the warp of the gas barrier film and improve the flatness, balance the stress of each inorganic thin film layer on the front and back surfaces, or balance the stress of the inorganic thin film layer on one side and the coating layer under it. Alternatively, the residual stress of the inorganic thin film layer itself may be reduced, or these may be combined to balance the stresses on both sides. The stress can be adjusted by the film forming pressure at the time of forming the inorganic thin film layer, the film thickness, the degree of curing shrinkage at the time of forming the coating layer, and the like.

(Moisture vapor transmission rate)
The water vapor transmission rate of the gas barrier film at 40 ° C. and 90% RH can be 0.1 g / m ² / day or less, and may be 0.001 g / m ² / day or less. Moisture vapor transmission rate can be measured by the Ca corrosion test method according to ISO / WD 15106-7 (Annex C).

(Manufacturing of gas barrier film)
The gas barrier film can be produced by a method of separately producing and bonding a base material layer and an inorganic thin film layer, a method of forming an inorganic thin film layer on the base material layer, or the like. The inorganic thin film layer is formed on the flexible base material or on the organic layer A laminated on the surface of the flexible base material by a known vacuum film forming method such as a CVD method using glow discharge plasma. It is preferable to manufacture. The organic layer B may be formed on the laminated film thus obtained by a known method. The inorganic thin film layer is preferably formed by a continuous film forming process, and more preferably, for example, the inorganic thin film layer is continuously formed on the long base material while being continuously conveyed. Specifically, the inorganic thin film layer may be formed while transporting the flexible base material from the delivery roll to the take-up roll. After that, the feed-out roll and the take-up roll may be inverted and the base material may be conveyed in the opposite direction to form an inorganic thin film layer from above.

(Adhesive layer)
The pressure-sensitive adhesive layer is placed on one surface of the gas barrier film. The pressure-sensitive adhesive layer is not particularly limited as long as it can exert a function of adhering the gas barrier film to other members, but in addition to the generally known adhesives and pressure-sensitive adhesives, adhesives and pressure-sensitive adhesives are used. A hygroscopic agent or a component that consumes water by reaction can be contained therein, or the component itself that consumes water by reaction can be used as an adhesive, an adhesive, or the like. Further, the pressure-sensitive adhesive layer can also remove the moisture adsorbed by drying, and in that case, it is preferable to use the pressure-sensitive adhesive layer in a dry state. The sex film 2 is bonded. The peelable film 2 is arranged on the gas barrier film via the pressure-sensitive adhesive layer. When the gas barrier film is adhered to another member, the releaseable film 2 is peeled off, and the other member is adhered to the pressure-sensitive adhesive layer arranged on the surface of the gas barrier film. At this time, the pressure-sensitive adhesive layer does not peel off from the gas barrier film when the peelable film 2 is peeled off.

The pressure-sensitive adhesive layer may be configured to be attached to an object by pressing, which is called a pressure-sensitive adhesive (PSA).

As the pressure-sensitive adhesive, a known pressure-sensitive adhesive can be used, and an adhesive that is "a substance that has adhesiveness at room temperature and adheres to an adherend with a light pressure" (JIS K 6800) is used. A capsule that is "an adhesive that contains a specific component in a protective film (microcapsule) and can maintain stability until the film is destroyed by appropriate means (pressure, heat, etc.)" (JIS K 6800). A mold adhesive may be used.

The pressure-sensitive adhesive layer has a polymerizable functional group remaining in the resin composition constituting the pressure-sensitive adhesive layer, and is strengthened by further polymerizing the resin composition constituting the pressure-sensitive adhesive layer after adhering the gas barrier film to other members. It may be configured to realize a good adhesion.

Further, the pressure-sensitive adhesive layer may be configured to polymerize and cure the resin by using a thermosetting resin composition or a photocurable resin composition as a material and supplying energy after the fact.

The thickness of the pressure-sensitive adhesive layer can be 100 μm or less. Further, when the thickness of the pressure-sensitive adhesive layer is less than 10 μm, it is assumed that the impact resistance is lowered and wrinkles are likely to occur. Therefore, it is preferably 10 μm or more.

The pressure-sensitive adhesive layer may be composed of one layer, or may have a laminated structure capable of adhering on both sides by providing adhesive layers on both sides of a film as a base material, such as a so-called double-sided tape. ..

(Removable film 1)
The peelable film 1 is releasably attached to the outermost layer of the laminated body of the present invention on the gas barrier film side. The peelable film 1 has a role as a protective film that protects the gas barrier film and other layers when the laminated body is stored, transported, and the like, and has a role of imparting support to the laminated body.

The peelable film 1 is preferably a plastic film from the viewpoint of easily enhancing the protection of the surface of the laminated body, and is, for example, polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), acrylic resin, polycarbonate (for example). It may be a resin film containing a resin such as PC) as a resin component. These resins may be used alone or in combination of two or more.

The peelable film 1 may be attached to the surface of the laminated body by electrostatic attraction or the like, or may be attached to the surface of the laminated body via an adhesive.

The adhesive for the protective film is, for example, acrylic resin, rubber resin, ethylene vinyl acetate copolymer resin, polyester resin, acetate resin, polyether sulfone resin, polycarbonate resin, polyamide resin, polyimide resin. , A polyolefin resin or the like is preferably contained as a pressure-sensitive adhesive. Further, the pressure-sensitive adhesive of the protective film may contain other components of the pressure-sensitive adhesive, such as an antistatic agent, a colorant, and an ultraviolet absorber.

The peelable film 1 has sufficient adhesiveness to maintain a state in which the peelable film 1 is bonded to the surface of the gas barrier film in, for example, a manufacturing process or a distribution process, and the peelable film 1 is formed from the surface of the laminated body. It is required to have a peelability that is easy to remove. The peel strength F1 between the peelable film 1 and the gas barrier film is preferably 0.1 N / cm or more, more preferably 0.1 N / cm or more, from the viewpoint of easily maintaining the state in which the peelable film 1 is bonded to the surface of the resin laminate. Has a peel strength of more than 0.1 N / cm, more preferably 0.15 N / cm or more, still more preferably 0.2 N / cm or more. Further, from the viewpoint of preventing the pressure-sensitive adhesive layer from peeling when the peelable film 1 is peeled from the surface of the gas barrier film, the peel strength F1 between the peelable film 1 and the gas barrier film is preferably 1.0 N. It is / cm or less, more preferably 0.7 N / cm or less, still more preferably 0.5 N / cm or less. The peel strength measurement between the peelable film 1 and the gas barrier film was carried out in accordance with JIS K 6854-2.

The peelable film 1 has a tensile elastic modulus of preferably 100 MPa or more, more preferably 150 MPa or more, still more preferably 200 MPa or more, from the viewpoint of easily enhancing the protective property of the surface of the laminated body. The tensile elastic modulus of the peelable film 1 is preferably 5,000 MPa or less, more preferably 4,500 MPa or less, and even more preferably 4,200 MPa or less, from the viewpoint of ease of bonding. The tensile elastic modulus of the peelable film can be measured by performing a tensile test using an electromechanical universal testing machine manufactured by Instron, using a test speed of 5 mm / min and a load cell of 5 kN according to JIS K 7127. can.

The average film thickness of the peelable film 1 is preferably 10 μm or more, more preferably 20 μm or more, still more preferably 30 μm or more, from the viewpoint of easily enhancing the protection of the surface of the laminated body. The average film thickness of the releaseable film 1 is preferably 100 μm or less, more preferably 80 μm or less, and further preferably 60 μm or less from the viewpoint of ease of bonding.
The average value of the film thickness of the peelable film 1 is measured by a digital micrometer, and the average value of the measured values at any 10 points is taken as the average value of the film thickness.

(Removable film 2)
The peelable film 2 is releasably attached to the surface of the pressure-sensitive adhesive layer of the laminate of the present invention.
The peelable film 2 has a role as a protective film that protects the pressure-sensitive adhesive layer and other layers when the laminated body is stored, transported, and the like, and has a role of imparting support to the laminated body. The peelable film 2 is peeled off from the surface of the pressure-sensitive adhesive layer of the laminated body in the manufacturing process of the display device, and the laminated body is bonded to the display device via the pressure-sensitive adhesive layer and incorporated as a component of the display device. ..

The peelable film 2 may be a paper, a plastic film, or the like. A release agent may be applied to the surface of the surface in order to enhance the release property.
The peelable film 2 is preferably a plastic film from the viewpoint of easily enhancing the protection of the surface of the pressure-sensitive adhesive layer, for example, polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), acrylic resin, polycarbonate. It may be a resin film containing a resin such as (PC) as a resin component. These resins may be used alone or in combination of two or more.

The peelable film 2 has sufficient adhesiveness to maintain a state in which the releaseable film 2 is attached to the surface of the pressure-sensitive adhesive layer in, for example, a manufacturing process or a distribution process, and the peelable film 2 is peelable from the surface of the pressure-sensitive adhesive layer. It is required to have a peelability that is easy to remove. The peel strength F2 between the peelable film 2 and the pressure-sensitive adhesive layer is preferably 0.05 N / cm or more, more preferably 0.05 N / cm or more, from the viewpoint of easily maintaining the state in which the peelable film 2 is bonded to the surface of the pressure-sensitive adhesive layer. Is a peel strength of 0.00.7 N / cm or more, more preferably 0.1 N / cm or more. Further, from the viewpoint that the peelable film 2 is preferably easily peeled off from the surface of the pressure-sensitive adhesive layer, the peeling strength F2 between the peelable film 2 and the pressure-sensitive adhesive layer is preferably 0.5 N / cm or less. , More preferably 0.4 N / cm or less, still more preferably 0.3 N / cm or less. The peel strength F2 is preferably lower than the peel strength F1 so that the peelable film 1 does not peel off when the peelable film 2 is peeled off in the bonding step with the display device. The peel strength measurement between the peelable film 2 and the pressure-sensitive adhesive layer was carried out in accordance with JIS K 6854-2.

The peelable film 2 has a tensile elastic modulus of preferably 100 MPa or more, more preferably 150 MPa or more, still more preferably 200 MPa or more, from the viewpoint of easily enhancing the protective property of the surface of the laminated body. The tensile elastic modulus of the peelable film 2 is preferably 5,000 MPa or less, more preferably 4,000 MPa or less, and even more preferably 4,000 MPa or less, from the viewpoint of ease of bonding. The tensile elastic modulus of the peelable film can be measured by performing a tensile test using an electromechanical universal testing machine manufactured by Instron, using a test speed of 5 mm / min and a load cell of 5 kN according to JIS K 7127. can.

The average film thickness of the peelable film 2 is preferably 10 μm or more, more preferably 20 μm or more, still more preferably 30 μm or more, from the viewpoint of easily enhancing the protection of the surface of the laminated body. The average film thickness of the releaseable film 2 is preferably 100 μm or less, more preferably 80 μm or less, and further preferably 60 μm or less from the viewpoint of ease of bonding.
The average value of the film thickness of the peelable film 2 is measured by a digital micrometer, and the average value of the measured values at any 10 points is taken as the average value of the film thickness.

(Laminated body)
The laminated body of the present invention satisfies the formulas (1) and (2).
F1 ≧ F2 (1)
(In the formula (1), F1 represents the peel strength between the peelable film 1 and the gas barrier film, and F2 represents the peel strength between the peelable film 2 and the pressure-sensitive adhesive layer.)
G1 / G2 ≧ 0.4 (2)
(In the formula (2), G1 represents the rigidity of the peelable film 1 and G2 represents the rigidity of the peelable film 2.)
Here, the rigidity of the peelable film is represented by the formula (a).
G∝E × T ³ (a)
(In the formula (a), E represents the elastic modulus (MD direction) of the peelable film, and T represents the thickness of the peelable film.)
Further, when F1 and F2 are equal in the equation (1) and G1 and G2 are equal in the equation (2), the equation (3) is satisfied.
T1> T2 (3)
(In the formula (3), T1 represents the thickness of the peelable film 1 and T2 represents the thickness of the peelable film 2.)
The laminate of the present invention satisfies the formulas (1) and (2), and if necessary, the formula (3), so that the peel strength F2 is lower than the peel strength F1 in the bonding step with the display device or the like. By doing so, it is possible to achieve a high yield without causing defects that occur when the film is attached to a display device or the like, for example, bubbles between the gas barrier film and the peelable film 1 and cracks in the gas barrier film. In the formula (1), when F1 = F2, peeling usually does not occur between the gas barrier film and the pressure-sensitive adhesive layer.
G1 / G2 is preferably 0.6 or more, more preferably 0.7 or more, still more preferably 0.8 or more, and particularly preferably 0.9 or more. G1 / G2 is preferably 4.5 or less, more preferably 4.0 or less, still more preferably 3.5 or less, and particularly preferably 3.0 or less.

The laminated body of the present invention may be in the form of being wound into a roll or in the form of a sheet cut to a predetermined size.

The laminate of the present invention can be bonded to the display device via the pressure-sensitive adhesive layer by peeling off the releaseable film 2 and exposing the pressure-sensitive adhesive layer in the bonding step with the display device.

FIG. 1 shows a schematic cross-sectional view of one form of the resin laminate of the present invention. In this laminate (10), the pressure-sensitive adhesive layer (5) is formed on a gas barrier film (4) in which an inorganic thin film layer (3) is formed on a flexible base material (1) having an organic layer A (2). The peelable film 1 (6) is attached to the surface opposite to the inorganic thin film layer (3), and the releaseable film 2 (7) is attached onto the pressure-sensitive adhesive layer (5). Note that FIG. 1 is an example of the laminated body of the present invention, and the laminated body of the present invention is not limited to this configuration. Examples of the layer structure of the laminated body of the present invention include a layer structure of a peelable film 2 / a pressure-sensitive adhesive layer / an inorganic thin film layer / an organic layer A / a flexible base material / a peelable film 1, and a peelable film 2 / adhesive. Agent layer / Inorganic thin film layer / Flexible base material / Organic layer A / Releasable film 1 layer structure, Releasable film 2 / Adhesive layer / Organic layer A / Flexible base material / Inorganic thin film layer / Removable Layer structure of film 1, peelable film 2 / pressure-sensitive adhesive layer / flexible base material / organic layer A / inorganic thin film layer / layer structure of peelable film 1, peelable film 2 / pressure-sensitive adhesive layer / inorganic thin film layer / Organic layer A / Flexible base material / Organic layer A / Releasable film 1 layer structure, Releasable film 2 / Adhesive layer / Organic layer B / Inorganic thin film layer / Organic layer A / Flexible base material / Organic The layer structure of the layer A / the peelable film 1 may be used.

(Manufacturing method of laminated body)
The laminate of the present invention can be produced by a known production method. Examples of the manufacturing method include a method of laminating a gas barrier film having a peelable film 1 and a pressure-sensitive adhesive layer having a peelable film 2, and a method of sticking a gas barrier film and a pressure-sensitive adhesive layer having a peelable film 2. A method of bonding the releaseable film 1 onto the gas barrier film 1 and a method of forming a pressure-sensitive adhesive layer on the gas barrier film having the releaseable film 1 and then attaching the releaseable film 2 to the pressure-sensitive adhesive layer. , A method of forming a pressure-sensitive adhesive layer on a gas barrier film and then attaching the releaseable film 1 and the releaseable film 2 to each other can be mentioned.

In the present invention, a method of laminating a gas barrier film having a peelable film 1 and a pressure-sensitive adhesive layer having a peelable film 2, a method of sticking a gas barrier film and a pressure-sensitive adhesive layer having a peelable film 2, and then peeling off. A method of attaching the sex film 1 onto the gas barrier film 1 and a method of forming a pressure-sensitive adhesive layer on the gas barrier film having the releaseable film 1 and then attaching the releaseable film 2 to the pressure-sensitive adhesive layer are preferable.

The gas barrier film having the peelable film 1 is, in addition to the peelable film 1, another peelable film different from the peelable film 1 (hereinafter, also referred to as another peelable film) before being bonded to the pressure-sensitive adhesive layer. May have more). The other peelable film can be peeled off before the gas barrier film and the pressure-sensitive adhesive layer are bonded, so that the surface of the exposed gas barrier film and the pressure-sensitive adhesive layer can be bonded together.

The other peelable film and the gas barrier film may be attached via an adhesive. As another releaseable film and adhesive that can be used for the gas barrier film having the releaseable film 1, those exemplified above for the releaseable film 1 can be used.

When the gas barrier film having the release film 1 has another release film, the release strength F1'between the other release film and the gas barrier film is between the release film 1 and the gas barrier film. It is preferably smaller than the peel strength F1. Since F1'is smaller than F1, when the other peelable film is peeled from the gas barrier film, the peelable film 1 is suppressed from peeling, bubbles are generated, or the gas barrier film is broken. be able to.

The pressure-sensitive adhesive layer having the releaseable film 2 may further have another releaseable film different from the releaseable film 2 in addition to the releaseable film 2 before being bonded to the gas barrier film. The other peelable film can be peeled off before the gas barrier film and the pressure-sensitive adhesive layer are bonded, so that the surface of the exposed pressure-sensitive adhesive layer and the gas barrier film can be bonded together.

As another releaseable film that can be used for the pressure-sensitive adhesive layer having the releaseable film 2, the one exemplified above for the releaseable film 2 can be used.

When the pressure-sensitive adhesive layer having the peelable film 2 has another peelable film, the peel strength F2'between the other peelable film and the pressure-sensitive adhesive layer is between the peel-off film 2 and the pressure-sensitive adhesive layer. It is preferably smaller than the peel strength F2. Since F2'is smaller than F2, it is possible to prevent the peelable film 2 from being peeled off or bubbles to be generated when the other peelable film is peeled off from the pressure-sensitive adhesive layer.

The peelable films 1 and 2 may each be subjected to a known peeling treatment so as to obtain a desired peeling strength. Examples of the method of applying the peeling treatment include a method of applying a peeling agent to the surface of the peelable film.

To bond the gas barrier film and the pressure-sensitive adhesive layer, the gas barrier film wound up in a roll shape and the pressure-sensitive adhesive layer wound up in a roll shape are bonded together while being unwound, and then wound up in a roll shape. It can be performed in a roll-to-roll format, or it can be cut to a desired size without being wound into a roll after being bonded.

Further, after unwinding the gas barrier film wound into a roll shape, the surface thereof is coated with an adhesive forming an adhesive layer, and the releaseable film 2 is bonded to the surface, and then the roll-to-roll format is used. It can be rolled up or cut to the desired dimensions.

(Device with laminate)
The present invention also provides devices having the laminate of the present invention, such as flexible electronic devices. The laminate of the present invention can also be used as a flexible substrate for a flexible electronic device (for example, a flexible display) such as a liquid crystal display element, a solar cell, and an organic EL display.

Hereinafter, the present invention will be described in more detail with reference to specific examples.

<Film thickness of inorganic thin film layer>
An inorganic thin film layer is formed on a flexible substrate, and a step difference between the non-deposited part and the film-formed part is measured using a surf coder ET200 manufactured by Kosaka Laboratory Co., Ltd., and the film thickness (T) of the inorganic thin film layer is measured. ) Was asked.

<X-ray photoelectron spectroscopy measurement of the surface of the inorganic thin film layer>
The atomic number ratio of the surface of the inorganic thin film layer of the gas barrier film was measured by X-ray photoelectron spectroscopy (QuantaraSXM, manufactured by ULVAC-PHI). An AlKα ray (1486.6 eV, X-ray spot 100 μm) was used as the X-ray source, and a neutralizing electron gun (1 eV) and a low-speed Ar ion gun (10 V) were used for charge correction at the time of measurement. For post-measurement analysis, spectral analysis was performed using MultiPak V6.1A (ULVAC-PHI), and the bindings of Si 2p, O 1s, N 1s, and C 1s obtained from the measured wide scan spectrum. The surface atomic number ratio of C to Si was calculated using the peak corresponding to the energy. As the surface atomic number ratio, the average value of the values measured five times was adopted.

<Infrared spectroscopy of the surface of the inorganic thin film layer (ATR method)>
Infrared spectroscopy of the surface of the inorganic thin film layer of the laminated film is performed by a Fourier transform infrared spectrophotometer (FT / IR-, manufactured by Nippon Spectroscopy Co., Ltd.) equipped with an ATR attachment (PIKE MIRacle) that uses germanium crystals for the prism. It was measured by 460Plus). Infrared spectroscopic measurement is performed by using a cyclic cycloolefin film (Zeon Corporation, registered trademark ZF16) as a flexible base material and forming an inorganic thin film layer on the base material. A laminated film for use was obtained.

<Optical characteristics of laminated film>
The total light transmittance of the laminated film was measured by a direct reading haze computer (model HGM-2DP) manufactured by Suga Test Instruments Co., Ltd. After performing background measurement without a sample, the laminated film was set in the sample holder and the measurement was performed to determine the total light transmittance.

<Gas barrier property of laminated film>
The gas barrier property of the laminated film was measured by the Ca corrosion test method in accordance with ISO / WD 15106-7 (Annex C) under the conditions of a temperature of 40 ° C. and a humidity of 90% RH, and the water vapor transmission rate of the laminated film was determined. ..

<Peeling strength>
The peel strength measurement was carried out in accordance with JIS Z 0237: 2000. The peelable sheet and the adherend were attached so as not to allow air bubbles to enter, to obtain a laminate of the peelable sheet / adherend. This laminate was allowed to stand for 24 hours in an environment of a temperature of 23 ° C. and a humidity of 50% RH. After that, the adherend is cut to a width of 20 mm, surface-fixed to a SUS plate with an adhesive and fixed to the lower side of the tensile tester, the release sheet is bent 90 degrees and fixed to the chuck on the upper side of the tensile tester. The peel strength was measured by peeling at a tensile speed of 0.3 m / min in an environment of a temperature of 23 ° C. and a humidity of 50% RH.

<Thickness>
The thickness of the peelable film was taken as the average value of the measured values at any 10 points by a digital micrometer.

<Tension modulus>
The measurement was carried out by performing a tensile test using an electromechanical universal testing machine manufactured by Instron, using a test speed of 5 mm / min and a load cell of 5 kN according to JIS K 7127.

[Manufacturing Example 1]
A gas barrier film was manufactured using the manufacturing apparatus shown in FIG. That is, the resin film base material was attached to the delivery roll 11. Then, a magnetic field is applied between the film-forming roll 31 and the film-forming roll 32, and power is supplied to the film-forming roll 31 and the film-forming roll 32, respectively, between the film-forming roll 31 and the film-forming roll 32. A film-forming gas (a mixed gas of hexamethyldisiloxane (HMDSO) as a raw material gas and oxygen gas as a reaction gas (which also functions as a discharge gas)) is generated in such a discharge region. Was supplied, and an inorganic thin film was formed by the plasma CVD method under the following conditions to obtain a gas barrier film.
<Film formation conditions>
Supply amount of raw material gas: 50 sccm (Standard Cubic Centimeter per Minute)
Oxygen gas supply: 500 sccm
Vacuum degree in vacuum chamber: 1Pa
Power applied from the plasma generation power supply: 0.4 kW
Frequency of power supply for plasma generation: 70kHz
Film transport speed: 0.6 m / min
Number of passes: 6 times

The inorganic thin film layer of the obtained gas barrier film was subjected to infrared spectroscopic measurement under the above conditions. From the obtained infrared absorption spectrum, the absorption intensity ratio (I ₂ / I ₁ ) between the peak intensity (I ₁ ) existing in 950 to 1050 cm ^-1 and the peak intensity (I ₂ ) existing in 1240 to 1290 cm ^-1 . ) Was obtained, and it was I ₂ / I ₁ = 0.03. Further, when the absorption intensity ratio (I ₃ / I ₁ ) between the peak intensity (I ₁ ) existing in 950 to 1050 cm ^-1 and the peak intensity (I ₃ ) existing in 770 to 830 cm ^-1 is obtained, I ₃ / I ₁ = 0.36.
Further, when the absorption intensity ratio (I ₄ / I ₃ ) between the peak intensity (I ₃ ) existing in 770 to 830 cm ^-1 and the peak intensity (I ₄ ) existing in 870 to 910 cm ^-1 is obtained, I ₄ / I ₃ = 0.84.

The infrared absorption spectrum did not change even after UV _- O3 treatment or atmospheric pressure plasma treatment described later, and showed the above-mentioned absorption intensity ratio. In the obtained laminated film 1, in the region of 90% or more in the film thickness direction of the inorganic thin film layer, oxygen, silicon and carbon are in the order from the one having the largest atomic number ratio, and the carbon distribution curve in the film thickness direction. The absolute value of the difference between the maximum value and the minimum value of the atomic number ratio of carbon in the carbon distribution curve was 0.15 or more.

The XPS depth profile measurement result of the inorganic thin film layer in the obtained gas barrier film is shown in FIG. In addition, XPS depth profile measurement is performed, and the average atomic concentration in the thickness direction of each atom is obtained from the obtained distribution curves of silicon atom, oxygen atom and carbon atom, and then the average atomic number ratio C / Si and O / As a result of calculating Si, the average atomic number ratio was C / Si = 0.30 and O / Si = 1.73.

The thickness of the inorganic thin film layer in the obtained gas barrier film was 0.7 μm. Further, in the obtained gas barrier film, the water vapor transmission rate was 5.0 × ^10-5 g / ( ^m2 · day) under the conditions of a temperature of 40 ° C. and a humidity of 90% RH.

[Production Example 2 of Inorganic Thin Film Layer]
The AC power supplied between the electrode rolls was set to 0.6 kW, the displacement was adjusted so that the pressure in the vacuum chamber was 3 Pa, and the number of passes was set to 2 in the same manner as in Production Example 1. An inorganic thin film layer was formed on the substrate layer.

[Peeling process]
The laminate was suction-fixed so that one surface of the peelable film became the surface of the adsorption plate. After adjusting the knife position at the interface between the peelable film 2 and the pressure-sensitive adhesive layer at the corner of the fixed laminate, an insertion peeling start portion was prepared. Subsequently, the peelable film 2 was peeled from the peeling start portion toward the diagonally located corners using a peeling device. In the peeling step, peeling occurred at the interface between the peelable film 1 and the base material, air bubbles entered between the peelable film 1 and the base material during peeling, and cracks were generated in the gas barrier film, which were counted as process defects.

Example 1
One side of cycloolefin polymer film (COP film, thickness: 50 μm, width: 350 mm, manufactured by Nippon Zeon Co., Ltd., trade name "Zeonoa (registered trademark) film, ZF-16"), which is a flexible substrate, is treated with corona. Then, coating agent 1 (manufactured by Toyochem Co., Ltd., Rio Duras TYAB500LC3NS, containing particles) was applied by the gravure coating method, dried at 100 ° C. for 3 minutes, and then the integrated light amount was 500 mJ using a high-pressure mercury lamp. Ultraviolet rays were irradiated under the condition of / cm ² , and an organic layer A1 (easy slip layer) having a thickness of 1.5 μm was laminated. Next, after corona treatment is applied to the other surface of the COP film, coating agent 2 (Aronix (registered trademark) UV3701 manufactured by Toagosei Co., Ltd.) is applied by a gravure coating method and dried at 100 ° C. for 3 minutes. Then, using a high-pressure mercury lamp, ultraviolet rays are irradiated under the condition of an integrated light amount of 500 mJ / cm ² , and an organic layer A2 (flattening layer) having a thickness of 1.8 μm is laminated to form a laminated film as a base material layer. Obtained. The inorganic thin film layer 2 is laminated on the surface of the laminated film thus obtained on the organic layer A2 side under the conditions of Production Example 1, and further on the surface of the organic layer A1 side under the conditions of Production Example 2. Layer 1 was laminated to produce a gas barrier film. Next, a transparent double-sided adhesive tape 1 (manufactured by Lintec Co., Ltd., TL-430S-6, 30 μm thickness) was attached to the surface of the inorganic thin film layer 2 of the gas barrier film as an adhesive layer. Subsequently, as the release film 2, a PET film (manufactured by Toyobo Co., Ltd., E5100, thickness: 38 μm) is subjected to a mold release treatment so that the peel strength with the adhesive layer is 0.2 N / 20 mm. The surface was bonded to the pressure-sensitive adhesive layer. Further, a protective film 1 (SAT106T-JSL, PET 38 μm, manufactured by Sun A. Kaken Co., Ltd.) was bonded to the surface of the inorganic thin film layer 1 as a peelable film 1. Table 1 shows the results of measuring the peel strengths F1 and F2, the thickness of the base material, and the tensile elastic modulus (MD direction) of the base material. When the peeling step was carried out using the obtained laminate, the ratio (yield) of the products obtained without causing process defects was 95%.

Example 2
Instead of the protective film 1, an acrylic adhesive layer adjusted so that the peeling force from the inorganic thin film layer 1 is 0.4 N / 20 mm is formed on a PET film (manufactured by Toyobo Co., Ltd., E5100, thickness: 50 μm). A laminated body was produced in the same manner as in Example 1 except that the protective film 2 was used. Table 1 shows the results of measuring the peel strengths F1 and F2, the thickness of the base material, and the tensile elastic modulus (MD direction) of the base material. When the peeling step was carried out using the obtained laminate, the ratio (yield) of the products obtained without causing process defects was 100%.

Example 3
A laminate was produced in the same manner as in Example 1 except that the protective film 3 (manufactured by Sun A. Kaken Co., Ltd., NSA-35H, PET 50 μm) was used instead of the protective film 1. Table 1 shows the results of measuring the peel strengths F1 and F2, the thickness of the base material, and the tensile elastic modulus (MD direction) of the base material. When the peeling step was carried out using the obtained laminate, the ratio (yield) of the products obtained without causing process defects was 90%.

Comparative Example 1
As the peelable film 2, a PET film (manufactured by Toyobo Co., Ltd., E5100, thickness: 100 μm) that had been mold -released so that the peeling force from the adhesive layer was 0.2 N / 20 mm was bonded to the adhesive layer. A laminated body was produced in the same manner as in Example 1 except for the above. Table 1 shows the results of measuring the peel strengths F1 and F2, the thickness of the base material, and the tensile elastic modulus (MD direction) of the base material. When the peeling step was carried out using the obtained laminate, the ratio (yield) of the products obtained without causing process defects was 30%.

Comparative Example 2
A protective film 4 (manufactured by Sanei Kaken Co., Ltd., NSA-33T, PET 38 μm) was used instead of the protective film 1, and the release film 2 was separated so that the peeling force from the adhesive layer was 0.4 N / 20 mm. A laminate was produced in the same manner as in Example 1 except that a mold- treated PET film (manufactured by Toyobo Co., Ltd., E5100, thickness: 38 μm) was bonded to the pressure-sensitive adhesive layer. Table 1 shows the results of measuring the peel strengths F1 and F2, the thickness of the base material, and the tensile elastic modulus (MD direction) of the base material. When the peeling step was carried out using the obtained laminate, the ratio (yield) of the products obtained without causing process defects was 0%.

Comparative Example 3
Instead of the protective film 1, an acrylic adhesive layer adjusted to have a peeling force of 0.1 N / 20 mm from the inorganic thin film layer 1 was formed on a PET film (manufactured by Toyobo Co., Ltd., E5100, thickness: 38 μm). A laminate was produced in the same manner as in Example 1 except that the protective film 5 was used. Table 1 shows the results of measuring the peel strengths F1 and F2, the thickness of the base material, and the tensile elastic modulus (MD direction) of the base material. When the peeling step was carried out using the obtained laminate, the ratio (yield) of the products obtained without causing process defects was 0%.

Comparative Example 4
A protective film 6 (7332, PE, 50 μm manufactured by Toray Film Processing Co., Ltd.) is used instead of the protective film 1, and the release film 2 has a peeling force of 0.4 N / 20 mm from the adhesive layer. A laminate was produced in the same manner as in Example 1 except that a release - treated PET film (manufactured by Toyobo Co., Ltd., E5100, thickness: 38 μm) was bonded to the pressure-sensitive adhesive layer. Table 1 shows the results of measuring the peel strengths F1 and F2, the thickness of the base material, and the tensile elastic modulus (MD direction) of the base material. When the peeling step was carried out using the obtained laminate, the ratio (yield) of the products obtained without causing process defects was 0%.

As shown in Table 1, in the laminates of the present invention shown in Examples 1 to 3, the peel strength F1 between the peelable film 1 and the gas barrier film is the peeling strength between the peelable film 2 and the pressure-sensitive adhesive layer. Since it is F2 or more and the rigidity G1 of the peelable film 1 is the rigidity G2 or more of the peelable film 2, bubbles or cracks in the gas barrier film 1 between the gas barrier film and the peelable film 1 in the peeling step. It was confirmed that the process defects such as the occurrence of the above were suppressed and the yield of the product was high. Therefore, it is understood that the laminate of the present invention is suitably used in display devices and the like.

1 Flexible base material 2 Organic layer A
3 Inorganic thin film layer 4 Gas barrier film 5 Adhesive layer 6 Detachable film 1
7 Detachable film 2
10 Laminated body 11 Feeding roll 21, 22, 23, 24 Conveying roll 31, 32 Film forming roll 41 Gas supply pipe 51 Plasma generation power supply 61, 62 Magnetic field generator 71 Winding roll 100 film

Claims (7)

A release film 1 having a gas barrier film, a pressure-sensitive adhesive layer on one surface of the gas barrier film, and a pressure-sensitive adhesive layer on the other surface of the gas barrier film, and a side opposite to the gas barrier film side of the pressure-sensitive adhesive layer. A laminate having a releaseable film 2 whose surface has been subjected to a mold release treatment .
The gas barrier film has a base material layer containing at least a flexible base material and an inorganic thin film layer on one surface of the base material layer.
Equation (1):
F1 ≧ F2 (1)
(In the formula (1), F1 represents the peeling strength between the peelable film 1 and the gas barrier film, and is 0.1 N / cm or more and 1.0 N / cm or less, and F2 is the peelable film 2 and the pressure-sensitive adhesive. Represents the peeling strength between layers and is 0.05 N / cm or more and 0.5 N / cm or less )
And equation (2):
G1 / G2 ≧ 0.4 (2)
(In the formula (2), G1 represents the rigidity of the peelable film 1 and G2 represents the rigidity of the peelable film 2).
A laminate that meets the requirements. The laminate according to claim 1, wherein the inorganic thin film layer contains a silicon atom, an oxygen atom, and a carbon atom. The laminate according to claim 1 or 2 , wherein the base material layer has an organic layer A on at least one surface of a flexible base material. The laminate according to claim 2 or 3 , wherein the atomic number ratio of carbon atoms to the total number of silicon atoms, oxygen atoms and carbon atoms contained in the inorganic thin film layer changes continuously in the thickness direction of the inorganic thin film layer. body. In the inorganic thin film layer, the average atomic number ratio of carbon atoms (C) to silicon atoms (Si) in the inorganic thin film layer is the formula (4) :.
0.10 <C / Si <0.50 (4)
The laminate according to any one of claims 2 to 4 , which is in the range of. The distance from the surface of the inorganic thin film layer in the film thickness direction of the inorganic thin film layer, the atomic number ratio of silicon to the total number of silicon atoms, oxygen atoms and carbon atoms contained in the inorganic thin film layer at each distance, and oxygen. In the silicon distribution curve, oxygen distribution curve, and carbon distribution curve, which show the relationship between the atomic number ratio of carbon and the atomic number ratio of carbon, conditions (i) and (ii):
(I) The condition represented by the formula (8) is satisfied in the region where the atomic number ratio of silicon, the atomic number ratio of oxygen and the atomic number ratio of carbon are 90% or more in the film thickness direction of the inorganic thin film layer.
Atomic number ratio of oxygen> Atomic number ratio of silicon> Atomic number ratio of carbon (8)
(Ii) The laminate according to any one of claims 2 to 5 , wherein the carbon distribution curve satisfies at least one extremum. A device comprising the laminate according to any one of claims 1 to 6 .

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