CN113165335A

CN113165335A - Laminate, method for producing same, and electronic device provided with same

Info

Publication number: CN113165335A
Application number: CN201980077881.8A
Authority: CN
Inventors: 牧岛幸宏; 畠泽翔太; 井宏元
Original assignee: Konica Minolta Inc
Current assignee: Konica Minolta Inc
Priority date: 2018-11-30
Filing date: 2019-11-28
Publication date: 2021-07-23
Also published as: WO2020111174A1; JPWO2020111174A1; KR20210060578A

Abstract

The problem of the present invention is to provide a laminate which can be made thin, prevents film cracking, is easily flexible and foldable, and has gas barrier properties for improving optical characteristics, a method for producing the laminate, and an electronic device provided with the laminate. The laminate of the present invention comprises at least an adhesive layer and a gas barrier layer, wherein the gas barrier layer contains an inorganic material, and a solvent permeation preventing layer containing a photo-or thermosetting resin is disposed between the adhesive layer and the gas barrier layer.

Description

Laminate, method for producing same, and electronic device provided with same

Technical Field

The present invention relates to a laminate, a method for producing the same, and an electronic device provided with the laminate, and more particularly, to a laminate and the like which can be made into a thin film, prevents cracking of the film, is easily flexible and foldable for an electronic device, and further has gas barrier properties for improving optical characteristics.

Background

It is known that a transparent conductive film containing Indium Tin Oxide (ITO), silver (Ag), or copper (Cu) used in a touch panel sensor or the like is liable to react with moisture or oxygen in the air, and is oxidized and corroded, thereby seriously impairing the device characteristics. As a method of blocking the influence of moisture and oxygen, for example, protection by a transparent adhesive (Optical adhesive, also referred to as OCA: Optical Clear add active) containing an acrylic resin is generally employed. However, in this method, in order to sufficiently secure the electrode portion against moisture and oxygen in the air, it is necessary to increase the layer thickness of the adhesive layer (also referred to as a film thickness in the present invention), and as a result, problems such as a decrease in optical characteristics (for example, light transmittance) and an increase in material cost are caused. In addition, thick films are also a great obstacle to recent unexpected flexibility and foldability due to cracking of the films.

On the other hand, as a technique for imparting gas barrier properties to an adhesive layer, a method of directly bonding a gas barrier film to the adhesive layer has been reported (for example, see patent documents 1 to 3), but the increase in thickness of the gas barrier film itself has also been a problem. In addition, in this method, a step of bonding the gas barrier film to the adhesive layer is required, which causes a problem of increasing the process load.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open No. 2006-160307

Patent document 2: japanese patent laid-open publication No. 2016-526077

Patent document 3: japanese patent No. 5239240

Disclosure of Invention

Technical problem to be solved by the invention

The present invention has been made in view of the above problems and circumstances, and an object of the present invention is to provide a laminate which can be made thin, prevents cracking of a film, is easily flexible and foldable for electronic devices, and further has gas barrier properties for improving optical characteristics.

Means for solving the problems

In order to solve the above problems, the present inventors have found that: by laminating a solvent permeation preventing layer containing a specific material and a gas barrier layer on the adhesive layer, a laminate which can be made thin, prevents film cracking, is easily flexible and foldable for electronic devices, and further has gas barrier properties with improved optical characteristics can be obtained.

That is, the above-described problem of the present invention is solved by the following means.

1. A laminate comprising at least an adhesive layer and a gas barrier layer, wherein,

the gas barrier layer contains an inorganic material, and,

a solvent permeation preventing layer containing a photo-or thermosetting resin is disposed between the adhesive layer and the gas barrier layer.

2. The laminate according to item 1, wherein,

the thickness of the solvent permeation prevention layer is within the range of 1-10000 nm.

3. The laminate according to

item

1 or 2, wherein,

the solvent permeation preventive layer contains at least a silicone-based resin, an acrylic-based resin, or an epoxy-based resin.

4. The laminate according to any one of items 1 to 3, wherein,

the solvent permeation preventive layer contains a silicone-based resin.

5. The laminate according to any one of items 1 to 4, wherein,

the surface of the solvent permeation preventive layer on the gas barrier layer side has a modified layer.

6. The laminate according to item 5, wherein,

the surface of the modified layer on the gas barrier layer side has a contact angle with water within a range of 20-100 DEG at a temperature of 23 ℃.

7. The laminate according to item 5 or 6, wherein,

the thickness of the modified layer is within the range of 1-70 nm.

8. The laminate according to any one of items 1 to 7, wherein,

the gas barrier layer contains polysilazane and a modified product thereof.

9. The laminate according to any one of items 1 to 8, wherein,

an organic metal oxide layer containing an organic metal oxide having a structure represented by the following general formula (A) is provided between the solvent permeation preventing layer and the gas barrier layer,

r- [ M (OR) of the general formula (A)₁)_y(O-)_x-y]_n-R

(wherein R represents a hydrogen atom, an alkyl group having 1 or more carbon atoms, an alkenyl group, an aryl group, a cycloalkyl group, an acyl group, an alkoxy group or a heterocyclic group; however, R may includeA fluorine atom as a substituent. M represents a metal atom. OR (OR)₁Represents a fluoroalkoxy group. x represents the valence of the metal atom and y represents any integer between 1 and x. n represents the degree of polycondensation. )

10. The laminate according to item 9, wherein,

the metal atom represented by M is selected from the group consisting of Si, Ti, Zr, Mg, Ca, Sr, Bi, Hf, Nb, Zn, Al, Pt, Ag and Au.

11. The laminate according to item 9 or 10, wherein,

the organic metal oxide layer contains at least a coating film in which sol-gel phase transfer has occurred.

12. The laminate according to any one of items 1 to 11, wherein,

the adhesive layer is provided with a peelable film on the side opposite to the solvent-repellent layer.

13. The laminate according to any one of items 1 to 11, wherein,

a peelable film is disposed on the side of the adhesive layer opposite to the solvent-resistant layer, and an adhesive layer is further disposed on the side of the gas barrier layer opposite to the solvent-resistant layer.

14. A method for producing a laminate provided with at least an adhesive layer and a gas barrier layer, the method comprising:

a step of applying a photo-or thermosetting resin to the surface of the adhesive layer to form a solvent permeation preventing layer containing the resin;

and a step of forming a gas barrier layer containing an inorganic material by coating the surface of the solvent permeation preventive layer with the inorganic material.

15. The method of manufacturing a laminate according to claim 14, further comprising, after the step of forming the solvent permeation preventive layer:

and (3) performing at least ultraviolet irradiation treatment, flash firing treatment, atmospheric pressure plasma treatment, plasma ion implantation treatment, or heating treatment on the solvent permeation preventive layer.

16. The method of manufacturing a laminate according to claim 14, further comprising, after the step of forming the solvent permeation preventive layer:

and a step of subjecting the solvent permeation preventive layer to ultraviolet irradiation treatment.

17. An electronic device is provided with:

the laminate according to any one of items 1 to 13.

ADVANTAGEOUS EFFECTS OF INVENTION

The means of the present invention can provide a laminate which can be made thin, prevents cracking of a film, is easily flexible and foldable for an electronic device, and has gas barrier properties for improving optical characteristics, a method for producing the laminate, and an electronic device provided with the laminate.

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

In the present invention, the solvent permeation preventing layer containing a photo-or thermosetting resin and the gas barrier layer containing an inorganic material such as polysilazane or a modified product thereof are laminated on the adhesive layer, whereby the effect of preventing the permeation of the solvent from the gas barrier layer can be exhibited.

The solvent permeation preventing layer contains a siloxane resin, and the surface of the solvent permeation preventing layer is modified by ultraviolet irradiation treatment, flash firing treatment, atmospheric pressure plasma treatment, plasma ion implantation treatment, heat treatment, or the like to have a modified layer containing a modified product of the siloxane resin, whereby the solvent permeation preventing layer and the gas barrier layer containing polysilazane and its modified product on the upper layer have the same modified product, and the adhesion is greatly improved. In addition, by providing the solvent permeation preventive layer with a dense modified layer, an excellent effect of further preventing the permeation of the solvent from the gas barrier layer can be exhibited. By these effects, it is considered that a laminate in which damage to the adhesive layer due to penetration of a solvent during formation of the gas barrier layer by coating is completely prevented can be provided.

Here, a mechanism of damage of the electronic device by the coating material is further considered. For example, when observing the state of an organic EL element (hereinafter referred to as organic EL) when a common organic solvent is applied to the organic EL element, it is known that the organic EL element is dissolved or reacted, and that certain intermolecular interaction between the solvent and the organic EL element affects and damages the organic EL element. That is, it is considered that the reason why the siloxane-based resin does not damage electronic devices is that the electronic devices are not subjected to intermolecular interaction.

Siloxane-based resins are known to contain Si-O bonds with a covalent bond radius of Si

About C

1.5 times, the rotational energy of the bonding is approximately 0. It can be seen that the bond is easy to rotate and the siloxane chain is very flexible. In addition, two of the 4 bonding arms of Si are bonded to a methyl group, and therefore, steric hindrance is high, and the structure is characterized by a helical structure. Since this helical structure is a repeating structure of siloxane bond 6 units, polarized dipoles (electronegativity is Si (1.8), C (2.5), and O (3.5), and therefore Si — O bonds have higher ionic bond properties than C — O bonds and C — C bonds, and have about 50% ionic properties) of siloxane bonds cancel each other, and polydimethylsiloxane is considered to be nonpolar. That is, it is considered that the siloxane-based resin and the electronic device do not interact with each other molecularly due to the non-polarity of the helical structure, thereby avoiding damage.

The silicone-based resin, as described above, does not impregnate the lower layer by itself, and has a property of preventing penetration of a solvent of the gas barrier layer of the upper layer. By utilizing this property, it is possible to directly apply an electronic device such as an organic EL, a touch panel sensor, and an organic thin film transistor described in japanese patent application No. 2018-104204, and the effect of the invention is excellent from the viewpoint of being also usable as a UV-curable adhesive without damage to the electronic device for bonding the electronic device and the gas barrier layer. Further, a function as a planarization layer described later can be imparted by surface treatment with vacuum ultraviolet light.

With the structure of the present invention, the gas barrier layer can be formed as a thin film directly on the adhesive layer, and the film can be made thin, and the film can be prevented from cracking, and the flexibility and foldability of the electronic device and the optical characteristics can be improved.

Drawings

FIG. 1A is a sectional view showing an example of a laminate of the present invention

FIG. 1B is a sectional view showing an example of a laminate of the present invention

FIG. 1C is a sectional view showing an example of a laminate of the present invention

FIG. 1D is a sectional view showing an example of a laminate of the present invention

FIG. 1E is a sectional view showing an example of a laminate of the present invention

FIG. 2A is a schematic view showing a manufacturing flow of a touch panel sensor

FIG. 2B is a schematic view showing a manufacturing flow of a touch panel sensor

FIG. 2C is a schematic view showing a manufacturing flow of a touch panel sensor

FIG. 2D is a schematic view showing a manufacturing flow of a touch panel sensor

FIG. 3A is a schematic view showing a process for producing an organic electroluminescent element using paper/cloth

FIG. 3B is a schematic view showing a process for producing an organic electroluminescent element using paper/cloth

FIG. 3C is a schematic view showing a process for producing an organic electroluminescent element using paper/cloth

FIG. 3D is a schematic view showing a process for producing an organic electroluminescent element using paper/cloth

FIG. 4 is a sectional view showing a solar cell including a bulk heterojunction type organic photoelectric conversion element

FIG. 5A is a view showing an example of the structure of an organic thin film transistor

FIG. 5B is a view showing an example of the structure of an organic thin film transistor

FIG. 5C is a view showing an example of the structure of an organic thin film transistor

FIG. 5D is a view showing an example of the structure of an organic thin film transistor

FIG. 5E is a view showing an example of the structure of an organic thin film transistor

FIG. 5F is a view showing an example of the structure of an organic thin film transistor

FIG. 6 is a standard graph showing the state of a grid in a crosscut test

Detailed description of the invention

The laminate of the present invention comprises at least an adhesive layer and a gas barrier layer, wherein the gas barrier layer contains an inorganic material, and a solvent permeation preventing layer containing a photo-or thermosetting resin is disposed between the adhesive layer and the gas barrier layer. This feature is a common or corresponding feature in the following embodiments.

The laminate of the present invention is characterized by being a laminate formed of a solvent permeation preventing layer capable of preventing permeation of a solvent from an inorganic material in a coating step and a gas barrier layer containing the inorganic material on the adhesive layer. In the case of the laminate of the present invention, when the gas barrier layer is formed on the adhesive layer, the conventional operations such as film formation by CVD (chemical vapor deposition method), adhesion of a gas barrier film, and the like are not required, and therefore, the apparatus and material costs can be reduced, and the productivity can be significantly improved. For example, since the production is always performed by a wet coating method, a thin-film laminate can be produced in a short delivery period as compared with the conventional one.

In the embodiment of the present invention, from the viewpoint of the effect of the present invention, when the thickness of the solvent permeation preventive layer is in the range of 1 to 10000nm, the solvent permeation from the gas barrier layer in the coating step can be prevented, and the reduction in thickness and the flexibility are not hindered, which is preferable.

In addition, from the viewpoint of improving adhesion to the inorganic material-containing gas barrier layer of the present invention, the solvent permeation preventing layer preferably contains a silicone-based resin, an acrylic-based resin, or an epoxy-based resin, and more preferably contains a silicone-based resin. In particular, it is preferable from the viewpoint of improving the adhesion to a gas barrier layer containing perhydropolysilazane (hereinafter referred to as PHPS) and its modified product, tetraethoxysilane (hereinafter referred to as TEOS), or perhydrosilsesquioxane, which is preferable as a material of the gas barrier layer of the present invention.

From the viewpoint of preventing permeation of a solvent of PHPS, it is preferable that the gas barrier layer-side surface of the solvent permeation preventive layer of the present invention has a modified layer, and from the viewpoint of further exhibiting this effect, an embodiment in which the gas barrier layer-side surface of the modified layer has a contact angle with water within a range of 20 ° to 100 ° at a temperature of 23 ℃ is preferable. In addition, from the viewpoint of preventing the permeation of a solvent and improving the adhesion between the solvent permeation preventing layer and the gas barrier layer, the thickness of the modified layer is preferably in the range of 1 to 70 nm.

Further, instead of the modified layer or as an upper layer thereof in the present invention, an organic metal oxide layer having an equivalent function may be provided. Specifically, the metal alkoxide is preferably a metal alkoxide obtained by coordination substitution of a fluorinated alcohol, and is preferably an organic metal oxide layer containing an organic metal oxide having a structure represented by the general formula (a), and the organic metal oxide layer is preferably an organic metal oxide layer on which a coating film is formed by a sol-gel method. As the metal, it is preferably selected from Si, Ti, Zr, Mg, Ca, Sr, Bi, Hf, Nb, Zn, Al, Pt, Ag and Au. The metal alkoxide is preferably used not only for promoting modification and improving adhesion at the time of lamination by a catalytic effect on the solvent permeation preventive layer and the gas barrier layer, but also for being excellent in production suitability because of having air-stable characteristics due to coordinate substitution with a fluorinated alcohol.

In addition, from the viewpoint of handling properties of the laminate of the present invention, it is preferable that the adhesive layer is provided with a peelable film on the side opposite to the solvent permeation preventive layer.

In addition, when the gas barrier film has such a layer structure, it is preferable to form an adhesive layer on the gas barrier layer, and the gas barrier film can be further bonded through the adhesive layer, which is preferable from the viewpoint of further improving the gas barrier property.

The method for producing a laminate of the present invention comprises: and a step of forming a solvent permeation preventing layer by applying a photo-or thermosetting resin to the surface of the adhesive layer, and a step of forming a gas barrier layer containing an inorganic material by applying an inorganic material to the surface of the solvent permeation preventing layer.

Preferably, the solvent permeation preventing layer is formed by: and a step of subjecting the surface of the solvent permeation preventive layer to ultraviolet irradiation treatment, flash combustion treatment, atmospheric pressure plasma treatment, plasma ion implantation treatment, or heating treatment. Among these, the ultraviolet irradiation treatment is a preferable production method from the viewpoint of forming a modified layer on the surface of the solvent permeation preventing layer, suppressing the solvent permeation to the adhesive layer at the time of forming the gas barrier layer, and improving the adhesion between the adhesive layer and the gas barrier layer.

The electronic device preferably includes the laminate of the present invention, from the viewpoint of preventing film cracking, improving flexibility and foldability of the electronic device, improving optical characteristics of the electronic device, and reducing process cost.

The present invention and its constituent elements, and specific embodiments and forms of the present invention will be described in detail below. In the present application, "to" is used in the sense of including numerical values described before and after the "to" as the lower limit value and the upper limit value.

Outline of laminate of the present invention

The laminate of the present invention comprises at least an adhesive layer and a gas barrier layer, wherein the gas barrier layer contains an inorganic material, and a solvent permeation preventing layer containing a photo-or thermosetting resin is disposed between the adhesive layer and the gas barrier layer.

The "gas barrier layer" in the present invention preferably has a water vapor transmission rate (25. + -. 0.5 ℃ C., relative humidity (90. + -. 2)%) of 0.01g/m as measured by a method based on JIS K7129-²Gas barrier properties of 24h or less. Further, it is preferable that the oxygen permeability measured by the method based on JIS K7126-1987 is 1X 10^-3mL/m²24h atm or less, and a water vapor transmission rate of 1X 10^-5g/m²High gas barrier properties of 24h or less.

The "photo-or thermosetting resin" in the present invention means a resin (polymer) having a property of being polymerized or crosslinked by light such as ultraviolet rays or heat to be cured. Polymerizable monomers (monomers) and oligomers having similar properties are also included.

The laminate of the present invention is preferably transparent from the viewpoint of bonding to an electronic device, and the light transmittance measured at a light wavelength of 450nm using a spectrophotometer U-4100 manufactured by HITACHI HIGH-TECHNOLOGIES corporation is preferably 70% or more, more preferably 80% or more, and particularly preferably 90% or more.

First, an embodiment of the present invention will be described with reference to the drawings.

FIG. 1 is a schematic view showing the structure of a laminate of the present invention. However, this is an example, and the present invention is not limited thereto.

FIG. 1A shows the basic structure of the laminate of the present invention. The laminate (1) has a structure in which a solvent permeation preventing layer (3) containing a photo-or thermosetting resin and a gas barrier layer (4) are disposed on an adhesive layer (2).

Fig. 1B is a sectional view of the solvent permeation preventive layer (3) according to the present invention, in which the reformed layer (5) is formed on the gas barrier layer (4) side, and it is preferable that after the solvent permeation preventive layer (3) is formed, a step of performing ultraviolet irradiation treatment, flash firing treatment, atmospheric pressure plasma treatment, plasma ion implantation treatment, or heat treatment on the surface of the solvent permeation preventive layer is added to form the reformed layer (5).

Fig. 1C shows a configuration in which an organic metal oxide layer (6) having a function equivalent to that of the reforming layer is disposed on the gas barrier layer (4) side of the solvent permeation preventive layer (3) of the present invention, and the organic metal oxide layer (6) is preferably formed as a coating film by a sol-gel method.

Fig. 1D shows a structure in which the laminate (1) of the present invention further has an adhesive layer (2) on the gas barrier layer (4), and this is a preferred embodiment in which a gas barrier film can be further bonded via the adhesive layer.

Fig. 1E shows a configuration in which a releasable film (7) is provided on the surface of the adhesive layer opposite to the solvent permeation preventive layer, and the adhesive layer (2) can be protected by the releasable film (7), thereby improving the handleability of the laminate (1) of the present invention.

Hereinafter, the constituent elements of the present invention will be described in detail.

[ 1] adhesive layer

The adhesive used in the adhesive layer is not particularly limited, and a general adhesive can be used, and among them, a synthetic resin adhesive is preferably used.

As the adhesive applicable to the present invention, a polyester adhesive, a urethane adhesive, a polyvinyl acetate adhesive, an acrylic adhesive, an epoxy adhesive, a nitrile rubber, or the like is used, and an adhesive containing a photocurable or thermosetting resin as a main component may be used.

The acrylic adhesive to be used may be any of a solvent-based adhesive and an emulsion-based adhesive, and from the viewpoint of easy improvement of the adhesive strength and the like, a solvent-based adhesive is preferable, and an adhesive obtained by solution polymerization is particularly preferable. Examples of raw materials for producing such a solvent-based acrylic adhesive by solution polymerization include acrylic esters such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and octyl acrylate as main monomers serving as a skeleton, vinyl acetate, acrylonitrile, styrene, and methyl methacrylate as comonomers for improving cohesive force, and methacrylic acid, acrylic acid, itaconic acid, hydroxyethyl methacrylate, and glycidyl methacrylate as functional group-containing monomers for promoting crosslinking, imparting stable adhesive force, and maintaining adhesive force to a certain extent even in the presence of water. In the adhesive layer, as a main monomer, a monomer having a high viscosity is particularly required, and therefore a monomer having a low glass transition temperature (Tg) such as butyl acrylate is particularly useful.

Examples of commercially available products of the acrylic adhesive include COPONIRU series (manufactured by japan synthetic chemical corporation).

In addition, in the formation of the curable adhesive layer, as the adhesive composition, for example, a radical curable adhesive can be suitably used. Examples of the radical curing adhesive include active energy ray curing adhesives such as electron beam curing adhesives and ultraviolet curing adhesives. In particular, an active energy ray-curable adhesive which can be cured in a short time is preferable, and an ultraviolet-curable adhesive which can be cured by low energy is more preferable.

Ultraviolet-curable adhesives can be roughly classified into: radical polymerization curing adhesives and cationic polymerization adhesives. In addition, a radical polymerization curing adhesive can be used as a thermosetting adhesive.

As the ultraviolet ray used for the curing, an LED light source emitting light in a wavelength range of 380 to 440nm, which is a gallium-sealed metal halide lamp, is preferable. For example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, an incandescent lamp, a xenon lamp, a halogen lamp, a carbon arc lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, a gallium lamp, an excimer laser, or sunlight can be used as a light source, and light having a wavelength shorter than 380nm can be blocked by a band-pass filter.

Examples of the curable component of the radical polymerization curable adhesive include a compound having a (meth) acryloyl group and a compound having a vinyl group. Any of monofunctional and bifunctional curable components can be used. These curable components may be used alone in 1 kind or in combination of 2 or more kinds. As these curable components, for example, compounds having a (meth) acryloyl group are suitable.

Examples of the curable component of the cationic polymerization curable adhesive include compounds having an epoxy group and an oxetane group. The compound having an epoxy group is not particularly limited as long as it has at least 2 epoxy groups in the molecule, and various curable epoxy compounds generally known can be used. Preferred epoxy compounds include: a compound having at least 2 epoxy groups and at least 1 aromatic ring in a molecule; a compound having at least 2 epoxy groups in the molecule and at least 1 of which is formed between adjacent 2 carbon atoms constituting an alicyclic ring, and the like.

In the present invention, an aqueous adhesive can be used, and as the aqueous adhesive, an adhesive containing a vinyl polymer is preferably used, and as the vinyl polymer, a polyvinyl alcohol resin is preferably used. Further, as the polyvinyl alcohol-based resin, an adhesive containing a polyvinyl alcohol-based resin having an acetoacetyl group is more preferable from the viewpoint of improving durability. As the crosslinking agent which can be blended with the polyvinyl alcohol resin, a compound having at least two functional groups reactive with the polyvinyl alcohol resin can be preferably used. Examples thereof include: boric acid, borax, carboxylic acid compounds, alkanediamines; isocyanates; epoxy resin; (ii) monoaldehydes; dialdehydes; an amino-formaldehyde resin; and salts of divalent or trivalent metals and oxides thereof.

Further, an adhesive commercially available as a sheet-like adhesive laminate can be preferably used. Such a sheet-like adhesive laminate is commercially available from MITSUI DUPONT POLYCHEMICA, 3M, AJINOMOTO, TESA, etc. Particularly, "NUCREL (registered trademark)" manufactured by MITSUI DUPON T polychemeica corporation (product numbers include AN4228C, N0903HC, N1525, AN4214C, AN4225C, AN42115C, N0908C, AN42012C, N410, N1035, N1050H, N1108C, H1110H, N1207C, N1214, AN4221C, N1560, N0200H, AN4213C, and N035C), and "3M optical Clear Adhesive" manufactured by 3M corporation (product numbers include 8171, 8172P, 8171CL, and 8172 CL).

The adhesive forming the adhesive layer may contain a suitable additive as necessary. Examples of additives include: coupling agents such as silane coupling agents and titanium coupling agents, adhesion promoters such as ethylene oxide, additives for improving wettability with transparent films, acryloxy compounds, additives for improving mechanical strength and processability such as hydrocarbons (natural and synthetic resins), ultraviolet absorbers, antioxidants, dyes, processing aids, ion traps, antioxidants, tackifiers, fillers (metal oxide particles), fillers containing water-absorbing polymers, plasticizers, leveling agents, foaming inhibitors, stabilizers such as antistatic agents, heat stabilizers and hydrolysis stabilizers.

The thickness of the adhesive layer is not particularly limited as long as the adhesive layer has a thickness within a range that provides desired adhesiveness, but is preferably within a range of 0.5 to 30 μm, and more preferably within a range of 5 to 25 μm, in consideration of the thickness and flexibility of the entire laminate.

In addition, an adhesive is preferably applied to the adhesive layer of the present invention.

As the adhesive, a pressure-sensitive adhesive is preferably used. When a pressure-sensitive adhesive is used, the electronic device can be bonded by applying pressure alone without using conditions such as heat and an organic solvent when forming an adhesive layer. The pressure-sensitive adhesive is roughly classified according to the kind of material, and examples thereof include: and adhesives including epoxy resins, acrylic resins, rubber resins, urethane resins, vinyl ether resins, silicone resins, and the like. Examples of the form of the adhesive include solvent type, emulsion type, and hot melt type. From the viewpoint of having more excellent cohesive force and elasticity, being able to maintain stable adhesiveness for a long time, and being more excellent in transparency, it is preferable to contain either an epoxy resin or an acrylic resin.

Specific examples of the acrylic resin include SK DYN E2147 manufactured by Suzuki chemical Co., Ltd, PD-S1 manufactured by PANAC Co., Ltd, and ZB7011W manufactured by DIC Co., Ltd.

Specific examples of the epoxy resin include Thre BOND1655 manufactured by the firm THERE BOND.

As shown in fig. 1(e), the adhesive layer of the present invention is preferably a peelable film (also referred to as a "separator") to improve handling properties.

The separator of the present invention is bonded to the adhesive layer so as to be peelable and is adjacent to the adhesive layer. Such a separator is not particularly limited as long as it can be bonded to the adhesive layer in a peelable manner.

Specific types of separators include, for example: a separator obtained by silicon coating, polyalkylene coating, or fluororesin coating on a substrate such as polyester, polyethylene, polypropylene, or paper is particularly preferably a separator obtained by silicon coating on a polyester film from the viewpoints of dimensional stability, smoothness, and peeling stability.

The thickness of the separator is preferably within a range of 10 to 100 μm, and more preferably within a range of 20 to 60 μm. The thickness of 10 μm or more is preferable because no transport wrinkle is generated in the film by heat during coating and drying, and the thickness of 100 μm or less is preferable from the viewpoint of economy.

[ 2] solvent permeation preventive layer

The solvent permeation preventing layer of the present invention is disposed between the adhesive layer and the gas barrier layer as a solvent permeation preventing layer containing a photo-or thermosetting resin.

The thickness of the solvent permeation preventive layer is preferably in the range of 1 to 10000nm, and in this range, it is preferable to prevent the permeation of the solvent from the gas barrier layer in the coating step and to prevent the reduction in thickness and the flexibility. Particularly, from the viewpoint of flexibility, the range of 1 to 500nm is more preferable.

The photo-or thermosetting resin is preferably a solvent-free resin. The "solvent-free resin" as used herein means a resin containing no solvent, and is preferably in a liquid state from the viewpoint of processability. In the case of the solvent-free type, deterioration due to solvent permeation from the solvent permeation preventing layer can be suppressed in the adhesive layer located below the solvent permeation preventing layer at the time of forming the solvent permeation preventing layer.

The solvent permeation preventing layer preferably contains a silicone resin, an acrylic resin, or an epoxy resin, and particularly preferably contains a silicone resin.

The solvent permeation preventing layer may be formed by an evaporation method using an organic material insoluble in a solvent or the like, but is preferably formed by coating. As the material formed by coating, a photocurable or thermosetting solventless monomer is preferably used, and particularly, a solventless photocurable polysiloxane monomer is preferably used. After the solvent-free monomer is coated, the coating is made into a solid film by photocuring and/or thermosetting to form a solvent permeation preventive layer.

The solvent permeation preventive layer may contain a getter for absorbing moisture and oxygen.

The solvent permeation preventive layer of the present invention can be formed by forming a coating liquid to which the solvent-free monomer liquid and a partially diluted solvent for viscosity adjustment are added between the electrode and the gas barrier layer of the present invention, and the forming method is not particularly limited, but coating by a wet forming method such as a spray coating method, a spin coating method, a blade coating method, a dip coater coating method, a casting method, a roll coating method, a bar coating method, a die coating method, a coating method using a dispenser or the like, a patterning method by a printing method including an inkjet printing method or the like is preferable. Among these, the inkjet printing method described later is preferable.

The thickness of the solvent permeation preventive layer of the present invention is preferably within a range of 10nm to 100 μm, more preferably 0.1 to 1 μm, in terms of a dried film, from the viewpoint of exhibiting the effects of stress relaxation, solvent permeation prevention from the gas barrier layer, and planarization.

As the light-or heat-curable resin, as the acrylic resin contained in the solvent permeation preventive layer, a polymer of a (meth) acrylate monomer is preferable, and as examples of the (meth) acrylate monomer, there can be preferably used: acrylate monomers such as methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, lauryl acrylate, and phenyl acrylate; methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, phenyl methacrylate, diethylaminoethyl methacrylate and dimethylaminoethyl methacrylate.

Similarly, examples of the epoxy resin contained in the solvent permeation preventive layer include: bisphenol epoxy resins such as bisphenol a epoxy resin and bisphenol F epoxy resin; an alicyclic epoxy resin; novolac type epoxy resins such as phenol novolac type epoxy resins and cresol novolac type epoxy resins; triphenol alkane type epoxy resins such as triphenol methane type epoxy resins and triphenol propane type epoxy resins; phenol aralkyl type epoxy resins, biphenyl aralkyl type epoxy resins, stilbene type epoxy resins, naphthalene type epoxy resins, biphenyl type epoxy resins, cyclopentadiene type epoxy resins, and the like. Among them, bisphenol type epoxy resins such as bisphenol a type epoxy resin and bisphenol F type epoxy resin are preferable from the viewpoint of exhibiting the effects of the present invention.

In addition, the solvent permeation preventing layer of the present invention preferably contains a siloxane-based resin from the viewpoint of adhesion to a gas barrier layer containing an inorganic material, in addition to the solvent permeation preventing function, and polydimethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, and the like can be used as the siloxane-based resin. Further, a siloxane containing a fluorine atom can be suitably used.

In particular, when the gas barrier layer contains polysilazane or a modified product thereof, it is preferable to contain a siloxane-based resin as the same material from the viewpoint of improving the adhesion.

The silicone resin used for the solvent permeation preventive layer of the present invention may be a low molecular weight material or a high molecular weight material. Particularly preferred are oligomers and polymers, and specific examples thereof include polysiloxane derivatives such as polysiloxane compounds, polydimethylsiloxane compounds, and polydimethylsiloxane copolymers. Further, these compounds may be combined.

The compound having a polysiloxane skeleton has a structure represented by the following general formula (I), and the effect of preventing penetration of a solvent can be arbitrarily controlled by changing the number of repetitions n (the number of 1 or more) in the general formula (I) and the type of the organic modified moiety.

[ chemical formula 1]

General formula (I)

Examples of the modification of n in the general formula (I) and the type of the organic modified moiety include a structure represented by the following general formula (II) (x and y are numbers of 1 or more representing the number of repetitions, and m is an integer of 1 or more), and the polysiloxane skeleton can be modified by providing a side chain. R in the general formula (II) is¹Examples thereof include methyl, ethyl and decyl. As R²Examples thereof include a polyether group, a polyester group, and an aralkyl group.

Further, a compound having a structure represented by the following general formula (III) (m is an integer of 1 or more) in which the polysiloxane chain contains a plurality of Si-O bonds and has a structure corresponding to R³An average of 1 polyether chain, etc.

In this way, in both of the compound having the structure represented by the general formula (II) and the compound having the structure represented by the general formula (III), control of the contact angle with water and adjustment of compatibility at the time of formation of the modified layer can be arbitrarily performed.

[ chemical formula 2]

General formula (II)

General formula (III)

(polysiloxanes)

Examples of the polysiloxane-based compound include: partial hydrolyzate of silane compound having hydrolyzable silyl group such as tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane, gamma-glycidoxypropylmethyldiethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-methacryloxypropyltriethoxysilane, gamma-methacryloxypropylmethyldimethoxysilane, gamma-methacryloxypropylmethyldiethoxysilane, gamma-acryloyloxypropyltrimethoxysilane, gamma-acryloyloxypropylmethyldimethoxysilane, etc, An organic silica sol obtained by stably dispersing fine particles of anhydrous silicic acid in an organic solvent, or an organic silica sol obtained by adding the above silane compound having radical polymerizability.

(Dimethylsiloxane-based Compound)

Examples of the polydimethylsiloxane-based compound include: polydimethylsiloxane, alkyl-modified polydimethylsiloxane, carboxyl-modified polydimethylsiloxane, amino-modified polydimethylsiloxane, epoxy-modified polydimethylsiloxane, fluorine-modified polydimethylsiloxane, and (meth) acrylate-modified polydimethylsiloxane (for example, GUV-235 manufactured by tokyo corporation).

(Dimethylsiloxane-based copolymer)

The polydimethylsiloxane-based copolymer may be any of a block copolymer, a graft copolymer, and a random copolymer, and is preferably a block copolymer or a graft copolymer.

(commercially available Material)

The commercially available material is not particularly limited as long as it has a silicon atom, and for example, the materials described below can be used.

Manufactured by Kyori chemical Co., Ltd.: GL-01, GL-02R, GL-03, GL-04R

Manufactured by Nissan chemical industries, Ltd.: SILFACE SAG002, SILFACE SAG005, SILFACE SAG008, SILFACE SAG503A, SURFYNOL 104E, SURFYNOL 104H, SURFYNOL 104A, SURFYNOL 104BC, SURFYNOL 104DPM, SURFYNOL 104PA, SURFYNOL 104PG-50, SURFYNOL 104S, SURFYNOL 420, SURFYNOL 440, SURFYNOL 465, SURFYNOL 485, SURFYNOL SE 50

Manufactured by shin-Etsu chemical industries, Ltd: FA-600, KC-89S, KR-500, KR-516, X-40-9296, KR-513, KER-4690-A/B, X-161A, X-22-162C, X-22-163, X-22-163A, X-22-164, X-22-164A, X-22-173BX, X-22-174ASX, X-22-176DX, X-22-343, X-22-2046, X-22-2445, X-22-3939A, X-22-9, X-22-4015, X-22-4272, X-22-4741, X-22-4952, X-22-6266, KF-50-100cs 40366, KF-96L-1cs, KF-101, KF-102, KF-105, KF-351, KF-352, KF-353, KF-354L, KF-355A, KF-393, KF-615A, KF-618, KF-857, KF-859, KF-860, KF-862, KF-877, KF-889, KF-945, KF-1001, KF-1002, KF-1005, KF-2012, KF-2201, X-22-2404, X-22-2426, X-22-3710, KF-6004, KF-1, KF-6015, KF-6123, KF-8001, KF-8010, KF-8012, X-22-9002

Manufactured by DOW CORNING TORAY: DOW CORNING 100F ADDITIVE, DOW CORNING 11ADDITIVE, DOW CORNING 3037INTERMEDIATE, DOW CORNING 56ADDITIVE, DOW CORNING TORAY Z-6094, DOW CORNING TORAY FZ-2104, DOW CORNING TORAY AY42-119, DOW CORNING TORAY FZ-2222

Manufactured by kao corporation: EMERGEN 102KG, EMERGEN 104P, EMERGEN 105, EMERGEN 106, EMERGEN 108, EMERGEN 109P, EMERGEN 120, EMERGEN 123P, EMERGEN 147, EMERGEN 210P, EMERGEN 220, EMERGEN 306P, EMERGEN 320P, EMERGEN 404, EMERGEN 408, EMERGEN 409PV, EMERGEN 420, EMERGEN 430, EMERGEN 705, EMERGEN 707, EMERGEN 709, EMERGEN 1108, EMERGEN 1118S-70, EMERGEN 1135S-70, EMERGEN 2020G-HA, EMERGEN 2025G, EMERGENLS-106, EMERGEN LS-110, EMERGEN LS114

The compound is preferably contained in an amount of 0.005 to 5% by mass based on the total components of the material constituting the solvent permeation preventive layer excluding the solvent.

The solvent permeation preventive layer of the present invention is preferably formed with a modified layer on the surface of the gas barrier layer by performing a step of ultraviolet irradiation treatment, flash firing treatment, atmospheric pressure plasma treatment, plasma ion implantation treatment, or heat treatment on the surface of the gas barrier layer after wet coating, and the contact angle of the surface of the modified layer with respect to pure water at a temperature of 23 ℃ is set to a range of 20 to 100 °, particularly from the viewpoint of improving adhesion. More preferably 20 to 50 degrees.

The contact angle can be measured by a known method. For example, the contact angle between the surface of the modified layer and a standard liquid (preferably pure water) is measured according to the method specified in JIS R3257. The measuring conditions are that the temperature is 25 +/-5 ℃, the humidity is 50 +/-10%, the dropping amount of the standard liquid is 1-4 mu L, and the time from the dropping of the standard liquid to the contact angle measurement is within 1 minute. As a specific procedure, about 1.5. mu.L of pure water as the standard liquid was dropped onto the sample at a temperature of 23 ℃ and 5 spots on the sample were measured by a solid-liquid interface analyzer (DropMaster500, manufactured by Kyowa interface science Co., Ltd.), and an average contact angle was obtained from the average of the measured values. The time until the contact angle was measured was within 1 minute from the dropping of the standard liquid.

From the viewpoint of exhibiting the effects of the stress relaxation property, the solvent permeation preventive property from the gas barrier layer, and the planarization property, the layer thickness of the modified layer is preferably in the range of 1 to 70nm, and more preferably in the range of 10 to 50 nm.

The modification treatment of the solvent permeation preventive layer in the present invention means a reaction of converting at least a part of the siloxane-based resin into silicon oxide, and the "modified layer" means a layer in which the average value of the carbon component ratio is 80 at% or less with respect to the average value of the carbon component ratio of the unmodified layer.

Therefore, the layer thickness of the modified layer can be determined by the following XPS analysis method and by elemental analysis in the layer thickness direction.

(XPS analysis method)

The XPS analysis here is a method of analyzing the constituent elements and the electronic states of a sample by irradiating the sample with X-rays and measuring the energy of generated photoelectrons.

The element concentration distribution curve (hereinafter referred to as "depth profile") in the thickness direction of the solvent permeation preventive layer of the present invention can be measured by combining measurement by X-ray photoelectron spectroscopy and rare gas ion sputtering with argon (Ar) or the like, exposing the surface of the solvent permeation preventive layer to the inside, and sequentially performing surface composition analysis to measure the element concentrations of silicon, oxygen, and carbon.

The profile obtained by XPS depth profile measurement can be prepared, for example, by setting the vertical axis as the atomic concentration ratio (unit: at%) of the element and the horizontal axis as the etching time (sputtering time). In the element distribution curve in which the horizontal axis represents the etching time as described above, since the etching time is approximately related to the distance from the surface of the solvent permeation preventing layer in the thickness direction of the solvent permeation preventing layer in the layer thickness direction, the "distance from the surface of the solvent permeation preventing layer in the thickness direction of the solvent permeation preventing layer" may be: the distance from the surface of the solvent permeation preventive layer was calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement. As the sputtering method used for such XPS depth profile measurement, it is preferable to use a rare gas ion sputtering method using argon (Ar) as an etching ion species, and to set the etching rate (etching rate) to 0.05nm/Sec (SiO) in the sputtering method₂Thermal oxide film equivalent).

Hereinafter, an example of specific conditions of XPS analysis applicable to composition analysis of the solvent permeation prevention layer of the present invention is shown.

An analysis device: QUANTERA SXM, manufactured by ULVAC-PHI Inc

X-ray source: mono-colorized Al-Ka

Sputtering ion: ar (3keV)

Depth profile: with SiO₂The sputtering thickness was converted, and the measurement was repeated at predetermined thickness intervals to obtain a depth profile in the depth direction. The thickness interval was set to 1nm (data per 1nm in the depth direction were obtained).

Quantification: the background was obtained by the Shirley method, and the area was quantified by the relative sensitivity coefficient method based on the obtained peak area. MultiPak manufactured by ULVAC-PHI corporation was used for data processing.

(ultraviolet ray irradiation treatment)

A preferable method for modifying the surface of the solvent permeation preventing layer of the present invention includes ultraviolet irradiation treatment. As the ultraviolet ray generating means, for example, as described above, there can be used: metal halide lamps, high pressure mercury lamps, low pressure mercury lamps, xenon arc clamps, carbon arc lamps, excimer lamps, UV light lasers, and the like.

Further, as one method of the ultraviolet irradiation treatment, a vacuum ultraviolet irradiation treatment may be mentioned. In the vacuum ultraviolet irradiation treatment, the illuminance of the vacuum ultraviolet on the coating surface of the silicone resin coating film is preferably 30 to 200mW/cm²More preferably 50 to 160mW/cm²Within the range of (1). Is 30mW/cm²In the above case, there is no risk of lowering the modification efficiency, and the modification efficiency is 200mW/cm²In the following cases, the coating film is preferably free from ablation and damage to the substrate.

The irradiation energy of the vacuum ultraviolet ray on the coating surface of the silicone resin layer is preferably 200 to 10000mJ/cm²More preferably 500 to 5000mJ/cm²Within the range of (1). When the amount is within this range, cracks and thermal deformation of the substrate do not occur.

The reaction during the ultraviolet irradiation requires oxygen, but the vacuum ultraviolet is absorbed by oxygen, so that the efficiency in the ultraviolet irradiation step is likely to be lowered, and therefore, the irradiation with vacuum ultraviolet is preferably performed 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 0.001 to 2.0 vol%, more preferably in the range of 0.005 to 0.5 vol%, and still more preferably in the range of 0.1 to 0.5 vol%.

The gas satisfying the irradiation atmosphere used in the vacuum ultraviolet irradiation is preferably a dry inert gas, and particularly preferably a dry nitrogen gas from the viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rate of the oxygen gas or the inert gas introduced into the irradiation chamber and changing the flow rate ratio.

The solvent permeation preventing layer containing a silicone resin or the like may be a single layer, and may have a laminated structure of 2 or more layers from the viewpoint of further improving the effect. When the multilayer structure is used, for example, a multilayer structure having a different type of silicon-containing polymer such as polysiloxane/polysilazane may be used. By changing the kind, the adhesion can be controlled in addition to the solvent permeation preventing function.

The solvent permeation preventive layer can be modified by xenon flash processing (flash processing) using a xenon lamp. As the discharge tube of the flash lamp used for the flash process, a discharge tube of xenon, helium, neon, argon, or the like can be used, and a xenon lamp is preferably used.

The preferred spectral band of the flash lamp is preferably in the range of 240 to 2000 nm. When the amount is within this range, damage such as thermal deformation of the substrate due to flash firing is less.

The light irradiation conditions of the flash lamp are optional, but the total light irradiation energy is preferably 0.1 to 50J/cm²More preferably 0.5 to 10J/cm²Within the range of (1). The light irradiation time is preferably in the range of 10. mu.s to 100 m.s, and more preferably in the range of 100. mu.s to 10 m.s. The number of light irradiation may be 1 or more, and is preferably in the range of 1 to 50. The light irradiation device of the flash lamp may be any device as long as the irradiation energy and the irradiation time are satisfied. In the case of the flash combustion in an atmosphere having a concentration of the oxygen-containing substance within the above-mentioned range, the flash combustion may be performed in an inert gas atmosphere of nitrogen, argon, helium, or the like. Examples of the xenon flash apparatus include "flash heating and high temperature firing flash lamp annealing" manufactured by USHIO Motor.

Further, from the viewpoint of forming a dense film, a method of plasma CVD treatment performed at or near atmospheric pressure is given as a preferable example. For example, the modification treatment of the solvent permeation preventive layer can be performed using an atmospheric pressure plasma discharge treatment apparatus constructed as described in Japanese patent laid-open No. 2004-68143.

In addition, the modification treatment of the solvent permeation preventive layer may be performed by a plasma ion implantation treatment.

A plasma ion implantation apparatus basically includes: a vacuum chamber, a microwave power supply, a magnet coil, and a direct current application device (pulse power supply).

The vacuum chamber is a container for placing a treatment object having a coating film of a solvent permeation preventive layer formed thereon at a predetermined position in the vacuum chamber and for ion-injecting the coating film.

The dc application device is a dc power supply and is a pulse power supply for applying a high-voltage pulse to the object to be treated.

In the plasma ion implantation apparatus having the above-described configuration, the microwave power source (plasma discharge electrode) and the magnet coil are driven to generate plasma of the gas introduced from the gas inlet around the conductor and the object to be treated.

Then, after a predetermined time has elapsed, the microwave power supply and the magnet coil are stopped from being driven, and the dc application device is driven to apply a high-voltage pulse (negative voltage) to the object to be treated via the high-voltage introduction terminal and the conductor.

Therefore, by applying such a high voltage pulse (negative voltage), ion species in the plasma are attracted, and ions are implanted into the coating film.

There is no particular limitation on the ion species. Examples thereof include: ions of rare gases such as argon, helium, neon, krypton, and xenon; ions of fluorocarbons, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, sulfur, and the like; ions of alkane gases such as methane, ethane, propane, butane, pentane, and hexane; ions of olefin gases such as ethylene, propylene, butene, and pentene; diene gas ions such as pentadiene and butadiene; acetylene gas-based ions such as acetylene and methylacetylene; ions of aromatic hydrocarbon gases such as benzene, toluene, xylene, indene, naphthalene, and phenanthrene; ions of cycloalkane gases such as cyclopropane and cyclohexane; ions of cyclic olefin gases such as cyclopentene and cyclohexene; ions of conductive metals such as gold, silver, copper, platinum, nickel, palladium, chromium, titanium, molybdenum, niobium, tantalum, tungsten, and aluminum; silane (SiH)₄) Or ions of organosilicon compounds, etc.

Of these, at least 1 type of ion selected from hydrogen, nitrogen, oxygen, argon, helium, neon, xenon, and krypton is preferable from the viewpoint of enabling easier implantation and obtaining excellent modification treatment.

The pressure of the vacuum chamber at the time of ion implantation, that is, the plasma ion implantation pressure, is preferably set to a value in the range of 0.01 to 1 Pa.

The voltage applied when plasma ions are implanted (high voltage pulse/negative voltage) is preferably set to a value in the range of-1 to-50 kV. More preferably, the voltage is set to a value in the range of-1 to-15 kV, and still more preferably, to a value in the range of-5 to-8 kV.

Specifically, the solvent permeation preventive layer was modified by using a plasma ion implantation apparatus (RF power source, manufactured by Nippon electronics Co., Ltd., RF56000, high voltage pulse power source, Tanshiki Kaisha, Ltd., PV-3-HSHV-0835).

Further, the modification treatment of the solvent permeation preventive layer may be performed by a heat treatment, preferably in combination with the various treatments and setting an appropriate temperature. For the heat treatment, a heating oven, an infrared heater, or the like can be used.

The solvent permeation preventive layer of the present invention may contain the same additives as the adhesive forming the adhesive layer, as required.

[ 3] an organic metal oxide layer

In the laminate of the present invention, an organic metal oxide layer having the same function may be provided as a modified layer in place of the solvent permeation preventive layer. Specifically, the organic metal oxide layer containing an organic metal oxide having a structure represented by the general formula (a) is preferable, and the organic metal oxide layer is preferably an organic metal oxide layer on which a coating film is formed by a sol-gel method, and the organic metal oxide is a metal alkoxide obtained by coordinate substitution with a fluorinated alcohol. The metal alkoxide is preferably used because it not only promotes modification and improves adhesion at the time of lamination by the catalytic effect on the solvent permeation preventive layer and the gas barrier layer, but also has air-stable characteristics by coordinate substitution with a fluorinated alcohol, and therefore, it is excellent in production suitability.

The organic metal oxide used is a monomer or a condensation polymer of the organic metal oxide obtained by adding an alcohol to decompose a metal alkoxide in the presence of an excess amount of the alcohol and substituting the alcohol. In this case, an organic metal oxide containing a fluorinated alkoxide is obtained by using a long-chain alcohol having a fluorine atom substituted at the β -position of a hydroxyl group.

On the other hand, the organic metal oxide can be sintered and irradiated with ultraviolet rays to promote a sol-gel reaction and form a condensation polymer. In this case, if a long-chain alcohol having a fluorine atom substituted at the β -position of the hydroxyl group is used, the water-repellent effect of fluorine decreases the frequency factor of moisture present around the metal in the metal alkoxide to decrease the hydrolysis rate, and this phenomenon is utilized to suppress the 3-dimensional polymerization reaction, whereby a dense organic metal oxide layer containing a desired organic metal oxide can be uniformly formed.

The organic metal oxide contained in the organic metal oxide layer of the present invention is a compound represented by the following reaction scheme I. In the structural formula of the sintered organometallic oxide polycondensate, the "M" in the "O — M" moiety has a substituent, but it is omitted.

[ chemical formula 3]

(reaction scheme I)

The organic metal oxide layer obtained by condensation polymerization of the organic metal oxide by sintering or ultraviolet irradiation is treated with water vapor (H) as a gas component from the outside of the system according to the following reaction scheme II₂O) hydrolysis, liberating the fluorinated alcohol (R' -OH), contributing to air stabilization.

In the following structural formulae, "M" in the "O — M" moiety further has a substituent, but is omitted.

[ chemical formula 4]

(reaction scheme II)

The organic metal oxide layer of the present invention preferably contains, as a main component, an organic metal oxide having a structure represented by the following general formula (a). The "main component" means that 70% by mass or more of the total mass of the organometallic oxide layer is the organometallic oxide which emits at least a water repellent substance or a hydrophobic substance, more preferably 80% by mass or more, and particularly preferably 90% by mass or more.

R- [ M (OR) of the general formula (A)₁)_y(O-)_x-y]_n-R

(wherein R represents a hydrogen atom, an alkyl group having 1 OR more carbon atoms, an alkenyl group, an aryl group, a cycloalkyl group, an acyl group, an alkoxy group OR a heterocyclic group; however, R may contain a fluorine atom as a substituent; M represents a metal atom; OR₁Represents a fluoroalkoxy group. x represents the valence of the metal atom and y represents any integer between 1 and x. n represents the degree of polycondensation. )

In addition, the fluorine ratio of the organometallic oxide layer of the present invention preferably satisfies the following formula (a).

F/(C + F) is more than or equal to 0.05 and less than or equal to 1.0 in the formula (a)

The meaning of the measurement of formula (a) is to convert a certain amount or more of fluorine atoms necessary for the organometallic oxide layer prepared by the sol-gel method into numerical values. F and C in the formula (a) represent the concentrations of fluorine atoms and carbon atoms, respectively.

The preferable range of the formula (a) is 0.2. ltoreq. F/(C + F). ltoreq.0.6.

The fluorine ratio is determined by applying a sol-gel solution used for forming an organic metal oxide layer on a silicon wafer to prepare a thin film, and then subjecting the thin film to element analysis by SEM EDS (Energy Dispersive X-ray spectroscopy) to determine the concentrations of fluorine atoms and carbon atoms, respectively. An example of the SEM EDS device is JSM-IT100 (manufactured by electronic division of Japan).

SEM and EDS analysis is characterized by being capable of detecting elements at high speed and high sensitivity with high accuracy.

The organic metal oxide of the present invention is not particularly limited as long as it can be produced by a sol-gel method, and examples thereof include metal oxides containing 1 or more metals selected from the group consisting of metals described in "science of sol-gel method" P13 and P20, silicon, lithium, sodium, copper, magnesium, calcium, bismuth, hafnium, niobium, strontium, barium, zinc, boron, aluminum, gallium, yttrium, silicon, germanium, lead, phosphorus, antimony, vanadium, tantalum, tungsten, lanthanum, neodymium, titanium, zirconium, platinum, silver and gold. From the viewpoint of obtaining the effects of the present invention, it is preferable that the metal atom represented by M is selected from the group consisting of silicon (Si), titanium (Ti), zirconium (Zr), magnesium (Mg), calcium (Ca), strontium (Sr), bismuth (Bi), hafnium (Hf), niobium (Nb), zinc (Zn), aluminum (Al), platinum (Pt), silver (Ag), and gold (Au).

In the general formula (A), OR₁Represents a fluoroalkoxy group.

R₁Represents an alkyl group, an aryl group, a cycloalkyl group, an acyl group, an alkoxy group, or a heterocyclic group, which is substituted with at least one fluorine atom. Specific examples of the substituents are as follows.

R represents a hydrogen atom, an alkyl group having 1 or more carbon atoms, an alkenyl group, an aryl group, a cycloalkyl group, an acyl group, an alkoxy group or a heterocyclic group. The hydrogen atoms of the respective groups may be at least partially substituted with a halogen atom. Further, it may be a polymer.

The alkyl group is substituted or unsubstituted, and specific examples thereof include methyl group, ethyl group, propyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, heneicosyl group, docosyl group, and the like, and a group having 8 or more carbon atoms is preferable. Further, these oligomers and polymers may be used.

The alkenyl group is substituted or unsubstituted, and specific examples thereof include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group, and a group having 8 or more carbon atoms may be preferable. Further, these oligomers and polymers may be used.

The aryl group is substituted or unsubstituted, and specific examples thereof include phenyl, tolyl, 4-cyanophenyl, biphenyl, o-terphenyl, m-terphenyl, p-terphenyl, naphthyl, anthryl, phenanthryl, fluorenyl, 9-phenylanthryl, 9, 10-diphenylanthryl, pyrenyl and the like, and a group having 8 or more carbon atoms may be preferable. Further, these oligomers and polymers may be used.

Specific examples of the substituted or unsubstituted alkoxy group include a methoxy group, an n-butoxy group, a tert-butoxy group, a trichloromethoxy group, a trifluoromethoxy group, and the like, and a group having 8 or more carbon atoms is preferable. Further, these oligomers and polymers may be used.

Specific examples of the substituted or unsubstituted cycloalkyl group include cyclopentyl, cyclohexyl, norbornyl, adamantyl, 4-methylcyclohexyl, and 4-cyanocyclohexyl groups, and a group having 8 or more carbon atoms is preferable. Further, these oligomers and polymers may be used.

Specific examples of the substituted or unsubstituted heterocyclic group include a pyrrolyl group, a pyrrolinyl group, a pyrazolyl group, a pyrazolinyl group, an imidazolyl group, a triazolyl group, a pyridyl group, a pyridazinyl group, a pyrimidinyl group, a pyrazinyl group, a triazinyl group, an indolyl group, a benzimidazolyl group, a purinyl group, a quinolyl group, an isoquinolyl group, a Shinorine group, a quinoxalyl group, a benzoquinolyl group, a fluorenylketone group, a dicyanofluorenylketone group, a carbazolyl group, an oxazolyl group, an oxadiazolyl group, a thiazolyl group, a thiadiazolyl group, a benzoxazolyl group, a benzothiazolyl group, a benzotriazolyl group, a dibenzoxazolyl group, a dibenzoimidazolyl group and the like. Further, these oligomers and polymers may be used.

Specific examples of the substituted or unsubstituted acyl group include formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, tert-valeryl, lauroyl, myristoyl, palmitoyl, stearoyl, oxalyl, malonyl, succinyl, glutaryl, adipyl, pimeloyl, suberoyl, azepinoyl, sebacoyl, acryloyl, propioloyl, methacryloyl, crotonyl, isocrotonyl, oleoyl, trans-oleoyl (elaidoyl), maleoyl, fumaroyl, citraconyl, mesoconyl, camphoryl, benzoyl, phthaloyl, isophthaloyl, terephthaloyl, naphthoyl, toluoyl, hydroantoyl, atroceroyl, cinnamoyl, furoyl, thenoyl, nicotinoyl, isonicotinoyl, nicotinoyl, camphoroyl, benzoyl, phthaloyl, isophthaloyl, and the like, Glycolyl, lactoyl, glyceryl, tartronyl, maloyl, tartaroyl, tropinoyl, diphenoxyacyl, salicyl, anisoyl, vanillyl, veratroyl, piperonyl, protocatechuiyl, galloyl, glyoxyl, pyruvoyl, acetoacetyl, mesooxalyl (meso-oxo), ketobutyryl (oxalacetate), oxalyl (oxalacetate), levulinoyl (levulinoyl) and levulinoyl (levulinoyl) groups, these acyl groups may be substituted with fluorine, chlorine, bromine, iodine and the like. The carbon number of the acyl group is preferably 8 or more. Further, these oligomers and polymers may be used.

Specific combinations of metal alkoxides, metal carboxylates, and fluorinated alcohols, which are used to form the organic metal oxide having the structure represented by general formula (a) of the present invention, are shown below. However, the present invention is not limited thereto.

The metal alkoxide, metal carboxylate and fluorinated alcohol (R' -OH) become the organo-metal oxide of the present invention by the following reaction scheme II I. Here, the (R' -OH) includes the following structures of F-1 to F-16.

[ chemical formula 5]

(reaction scheme III)

[ chemical formula 6]

Examples of the metal alkoxide or metal carboxylate of the present invention include the following M (OR)_nOr M (OCO R)_nThe organometallic oxide of the present invention is combined with the (R' -OH: F-1 to F-16) compound to form a compound having a structure represented by the following exemplary compound No. 1 to 135 (see the following exemplary compounds I, II and III). However, the organo-metal oxide of the present invention is not limited thereto.

[ chemical formula 7]

(exemplary Compound I)

Example Compound numbering	M(OR)_n	R′-OH
			1	Ti(OiPr)₄	F-1
2	Ti(OiPr)₄	F-2
			3	Ti(OiPr)₄	F-3
4	Ti(OiPr)₄	F-4
			5	Ti(OiPr)₄	F-5
6	Ti(OiPr)₄	F-6
			7	Ti(OiPr)₄	F-7
8	Ti(OiPr)₄	F-8
			9	Ti(OiPr)₄	F-9
10	Ti(OiPr₎4	F-10
			11	Ti(OiPr)₄	F-11
12	Ti(OiPr)₄	F-12
			13	Ti(OiPr)₄	F-13
14	Ti(OiPr)₄	F-14
			15	Ti(OiPr)₄	F-15
16	Ti(OiPr)₄	F-16
			17	Ti(OEt)₄	F-1
18	Ti(OEt)₄	F-2
			19	Ti(OEt)₄	F-3
20	Ti(OEt)₄	F-4
			21	Ti(OEt)₄	F-5
22	Ti(OEt)₄	F-6
			23	Ti(OEt)₄	F-7
24	Ti(OEt)₄	F-8
			25	Ti(OEt)₄	F-9
26	Ti(OEt)₄	F-10
			27	Ti(OEt)₄	F-11
28	Ti(OEt)₄	F-12
			29	Ti(OEt)₄	F-13
30	Ti(OEt)₄	F-14
			31	Ti(OEt)₄	F-15
32	Ti(OEt)₄	F-16
			33	Ti(OBu)₄	F-1
34	Ti(OBu)₄	F-2
			35	Ti(OBu)₄	F-3
36	Ti(OBu)₄	F-4
			37	Ti(OBu)₄	F-5
38	Ti(OBu)₄	F-6
			39	Ti(OBu)₄	F-7
40	Ti(OBu)₄	F-8
			41	Ti(OMe)₄	F-1
42	Ti(OMe)₄	F-2
			43	Ti(OMe)₄	F-5
44	Ti(OMe)₄	F-13
			45	Ti(OMe)₄	F-15

[ chemical formula 8]

(exemplary Compound II)

Example Compound numbering	M(OR)_n	R′-OH
			46	Zr(OiPr)₄	F-1
47	Zr(OiPr)₄	F-2
			48	Zr(OiPr)₄	F-5
49	Zr(OiPr)₄	F-13
			50	Zr(OiPr)₄	F-15
51	Sn(OtBu)₄	F-1
			52	Sn(OtBu)₄	F-2
53	Sn(OtBu)₄	F-5
			54	Sn(OtBu)₄	F-13
55	Sn(OtBu)₄	F-15
			56	Si(OEt)₄	F-1
57	Si(OEt)₄	F_-2
			58	Si(OEt)₄	F-5
59	Si(OEt)₄	F-13
			60	Si(OEt)₄	F-15
61	Si(OBu)₄	F-1
			62	Si(OBu)₄	F-2
63	Si(OBu)₄	F-5
			64	Si(OBu)₄	F-13
65	Si(OBu)₄	F-15
			66	Ta(OEt)₅	F-1
67	Ta(OEt)₅	F-2
			68	Ta(OEt)₅	F-5
69	Ta(OEt)₅	F-13
			70	Ta(OEt)₅	F-15
71	Yb(OiPr)₃	F-1
			72	Yb(OiPr)₃	F-2
73	Yb(OiPr)₃	F-5
			74	Yb(OiPr)₃	F-13
75	Yb(OiPr)₃	F-15
			76	Y(OiPr)₃	F-1
77	Y(OiPr)₃	F-2
			78	Y(OiPr)₃	F-5
79	Y(OiPr)₃	F-13
			80	Y(OiPr)₃	F-15
81	Al(OiPr)₃	F-1
			82	Al(OiPr)₃	F-2
83	Al(OiPr)₃	F-5
			84	Al(OiPr)₃	F-13
85	Al(OiPr)₃	F-15
			86	Al(OEt)₃	F-1
87	Al(OEt)₃	F-2
			88	Al(OEt)₃	F-5
89	Al(OEt)₃	F-13
			90	Al(OEt)₃	F-15

[ chemical formula 9]

(exemplary Compound III)

Example Compound numbering	M(OCOR)_n	R′-OH
			91	Zn(OCOCH₃)₂·2H₂O	F-1
92	Zn(OCOCH₃)₂·2H₂O	F-2
			93	Zn(OCOCH₃)₂·2H₂O	F-5
94	Zn(OCOCH₃)₂·2H₂O	F-13
			95	Zn(OCOCH₃)₂·2H₂O	F-15
96	Co(OCOCH₃)₂	F-1
			97	Co(OCOCH₃)₂	F-2
98	Co(OCOCH₃)₂	F-5
			99	Co(OCOCH₃)₂	F-13
100	Co(OCOCH₃)₂	F-15
			101	In(OCOCH₃)₃	F-1
102	In(OCOCH₃)₃	F-2
			103	In(OCOCH₃)₃	F-5
104	In(OCOCH₃)₃	F-13
			105	In(OCOCH₃)₃	F-15
106	Fe(OCOCH₃)₂	F-1
			107	Fe(OCOCH₃)₂	F-2
108	Fe(OCOCH₃)₂	F-5
			109	Fe(OCOCH₃)₂	F-13
110	Fe(OCOCH₃)₂	F-15
			111	Mo(OCOCH₃)₂	F-1
112	Mo(OCOCH₃)₂	F-2
			113	Mo(OCOCH₃)₂	F-5
114	Mo(OCOCH₃)₂	F-13
			115	Mo(OCOCH₃)₂	F-15
116	Ni(OCOCH₃)₂·4H₂O	F-1
			117	Ni(OCOCH₃)₂·4H₂O	F-2
118	Ni(OCOCH₃)₂·4H₂O	F-5
			119	Ni(OCOCH₃)₂·4H₂O	F-13
120	Ni(OCOCH₃)₂·4H₂O	F-15
			121	Pd(OCOCH₃)₂	F-1
122	Pd(OCOCH₃)₂	F-2
			123	Pd(OCOCH₃)₂	F-5
124	Pd(OCOCH₃)₂	F-13
			125	Pd(OCOCH₃)₂	F-15
126	Ag(OCOCH₃)	F-1
			127	Ag(OCOCH₃)	F-2
128	Ag(OCOCH₃)	F-5
			129	Ag(OCOCH₃)	F-13
130	Ag(OCOCH₃)	F-15
			131	Sr(OCOCH₃)₂	F-1
132	Sr(OCOCH₃)₂	F-2
			133	Sr(OCOCH₃)₂	F-5
134	Sr(OCOCH₃)₂	F-13
			135	Sr(OCOCH₃)₂	F-15

In the method for producing an organic metal oxide, which produces an organic metal oxide according to the present invention, the production is carried out using a mixed solution of a metal alkoxide and a fluorinated alcohol.

As an example of the reaction, reaction scheme IV of the exemplified compound No. 1 and the structure of the organic metal oxide when applied to the organic metal oxide layer are shown below.

In the following structural formula, "Ti" in the "O — Ti" portion further has a substituent, but is omitted.

[ chemical formula 10]

(reaction scheme IV)

The method for producing an organic metal oxide of the present invention includes: a method in which a fluorinated alcohol is added to a metal alkoxide or a metal carboxylate and the mixture is stirred and mixed, and then water and a catalyst are added as necessary to carry out a reaction at a predetermined temperature.

In order to promote the hydrolysis and polycondensation reaction in the sol-gel reaction, a catalyst which can be used for the hydrolysis and polymerization reaction, as shown below, may be added. The catalyst used as a catalyst for hydrolysis and polymerization of a sol-gel reaction is a catalyst used in a general sol-gel reaction described in "the latest functional thin film production technology by the sol-gel method" (Shimadzu, general technologies, Inc., P29), "science by the sol-gel method" (Katakutaki Kaisha, AGEN Kaifeng Co., Ltd., P154), and the like. Examples thereof include: examples of the acid catalyst include inorganic and organic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, tartaric acid and toluenesulfonic acid, alkali metal hydroxides such as ammonium hydroxide, potassium hydroxide and sodium hydroxide, 4-stage ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and tetrabutylammonium hydroxide, amines such as ammonia, triethylamine, tributylamine, morpholine, pyridine, piperidine, ethylenediamine, diethylenetriamine, ethanolamine, diethanolamine and triethanolamine, and aminosilanes such as 3-aminopropyltriethoxysilane and N- (2-aminoethyl) -3-aminopropyltrimethoxysilane.

The amount of the catalyst used is preferably 2 molar equivalents or less, more preferably 1 molar equivalent or less, based on 1 mole of the metal alkoxide or the metal carboxylate as the raw material of the organic metal oxide.

In the sol-gel reaction, the amount of water to be added is preferably 40 molar equivalents or less, more preferably 10 molar equivalents or less, and still more preferably 5 molar equivalents or less, based on 1 mole of the metal alkoxide or the metal carboxylate as the raw material of the organic metal oxide.

In the present invention, the reaction concentration, temperature and time of the sol-gel reaction are preferably related to the kind, molecular weight and conditions of the metal alkoxide or metal carboxylate to be used, and thus cannot be generally defined. That is, when the molecular weight of the alkoxide or the metal carboxylate is high or the reaction concentration is high, if the reaction temperature is set high or the reaction time is set too long, the molecular weight of the reaction product increases with hydrolysis or polycondensation reaction, and high viscosity or gelation may occur. Therefore, the reaction concentration is usually preferably 1 to 50%, more preferably 5 to 30%, based on the mass% concentration of the solid content in the solution. The reaction temperature is usually 0 to 150 ℃, preferably 1 to 100 ℃, more preferably 20 to 60 ℃ and the reaction time is preferably about 1 to 50 hours, although it depends on the reaction time.

The condensation polymer of the organic metal oxide forms an organic metal oxide layer, and absorbs moisture to form the following oligomer according to reaction scheme V below, which contributes to improvement of air stability. In addition, although there is a portion remaining as OR' in the layer, it does not remain so much as to affect the adhesion.

[ chemical formula 11]

(reaction scheme V)

The organo-metal oxide layer of the present invention may be formed by: the coating liquid containing the organic metal oxide of the present invention is prepared, coated on the solvent-repellent layer and polycondensed by sintering or irradiating ultraviolet rays, and simultaneously filmed.

As the organic solvent which can be used as needed when preparing the coating liquid, for example, a hydrocarbon solvent such as an aliphatic hydrocarbon, an alicyclic hydrocarbon, and an aromatic hydrocarbon, a halogenated hydrocarbon solvent, or an ether such as an aliphatic ether or an alicyclic ether can be suitably used.

The concentration of the organic metal oxide of the present invention in the coating liquid varies depending on the target thickness and the pot life of the coating liquid, but is preferably about 0.2 to 35% by mass. In the coating liquid, a catalyst for promoting polymerization is preferably added.

The coating liquid obtained by the preparation may be a wet forming method such as a coating method by a spray coating method, a spin coating method, a doctor blade coating method, a dip coater coating method, a casting method, a roll coating method, a bar coating method, a die coating method, or a patterning method including a printing method such as an inkjet printing method and a dispenser method, and may be used depending on the material. Preferred among these is an inkjet printing method. The inkjet printing method is not particularly limited, and a known method can be used.

The method of ejecting the coating liquid from the inkjet head by the inkjet printing method may be any of an on-demand method and a continuous method. The on-demand ink jet head may be any of an electro-mechanical conversion system such as a single chamber type, a double chamber type, a channel type, a piston type, a shared mode type, and a shared wall type, an electro-thermal conversion system such as a thermal ink jet type and a bubble jet (registered trademark) type, and the like.

For example, inkjet heads having a structure described in Japanese patent laid-open Nos. 2012-140017, 2013-010227, 2014-058171, 2014-097644, 2015-142979, 2015-142980, 2016-002675, 2016-002682, 2016-002401, 2017-109476, 2017-177626 and the like can be suitably selected.

In the case of immobilizing the organic metal oxide layer after coating, plasma, ozone, or ultraviolet light capable of performing a polymerization reaction at a low temperature is preferably used, and among these, ultraviolet light is preferred in order to improve the smoothness of the film surface.

As means for generating ultraviolet rays in the ultraviolet ray treatment, as described above, for example, a metal halide lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a xenon arc torch, a carbon arc lamp, an excimer lamp, a UV light laser, and the like can be given.

The ultraviolet irradiation can be suitably used for batch processing or continuous processing, and can be suitably selected depending on the shape of the substrate to be used. When the substrate on which the organic metal oxide layer is formed is a long film, the substrate can be transported and continuously irradiated with ultraviolet light in a drying zone provided with the ultraviolet light generating source. The time required for the ultraviolet irradiation depends on the composition and concentration of the substrate used and the coating liquid containing a drying agent, but is usually 0.1 second to 10 minutes, preferably 0.5 second to 3 minutes.

The energy received by the coating surface is preferably 1.0J/cm from the viewpoint of uniformly forming a strong thin film²Above, more preferably 1.5J/cm²The above. Also, from the viewpoint of avoiding excessive ultraviolet irradiation, it is preferably 14.0J/cm²Hereinafter, more preferably 12.0J/cm²The concentration is preferably 10.0J/cm or less²The following.

The oxygen concentration when ultraviolet light is irradiated is preferably 300 to 10000 ppm by volume (1% by volume), and more preferably 500 to 5000 ppm by volume. By adjusting the concentration of oxygen within such a range, it is possible to prevent oxygen in the organic metal oxide layer from becoming excessive and prevent deterioration of moisture absorption.

In the ultraviolet irradiation, a dry inert gas is preferably used as a gas other than oxygen, and particularly, a dry nitrogen gas is preferred from the viewpoint of cost.

For details of these ultraviolet treatments, for example, the descriptions in paragraphs 0055 to 0091 of Japanese patent laid-open No. 2012-086394, paragraphs 0049 to 0085 of Japanese patent laid-open No. 2012-006154, and paragraphs 0046 to 0074 of Japanese patent laid-open No. 2011-251460 can be referred to.

[ 4] gas barrier layer

The gas barrier layer of the present invention is preferably a layer obtained by modifying a layer obtained by applying and drying a coating liquid containing at least polysilazane (hereinafter, the gas barrier layer may be referred to as a polysilazane layer).

The thickness of the gas barrier layer after drying is preferably within a range of 5 to 1000nm, more preferably within a range of 10 to 800nm, and particularly preferably within a range of 50 to 500nm, from the viewpoint of achieving both sealing effect and flexibility.

(polysilazane)

Polysilazanes are polymers having a silicon-nitrogen bond, and are SiO having a bond of Si-N, Si-H, N-H or the like₂、Si₃N₄And intermediate solid solution of both SiO_xN_yAnd the like.

Specifically, the polysilazane preferably has a partial structure represented by the following general formula (1).

[ chemical formula 12]

General formula (1)

In the general formula (1), R₁、R₂And R₃Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, a vinyl group or a (trialkoxysilyl) alkyl group. At this time, R₁、R₂And R₃May be the same or different, respectively. Examples of the alkyl group include a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. More specifically, examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, cyclopropyl group, cyclopentyl group, and cyclohexyl group. The aryl group includes aryl groups having 6 to 30 carbon atoms. More specifically, examples thereof include non-condensed hydrocarbon groups such as phenyl, biphenyl, and terphenyl; pentenyl, indenyl, naphthyl, azulenyl, heptenyl, biphenylenyl, fluorenyl, acenaphthenyl, obsidian-enyl, acenaphthenyl, phenacenyl, phenanthrenyl, anthracenyl, fluoranthenyl, acephenanthrenyl, acenaphthenyl, triphenylenyl, pyrenyl, and the like,

Condensed polycyclic hydrocarbon groups such as mesityl and tetracenyl. Examples of the (trialkoxysilyl) alkyl group include alkyl groups having 1 to 8 carbon atoms and having a silyl group substituted with an alkoxy group having 1 to 8 carbon atoms. More specifically, 3- (triethoxysilyl) propyl group, 3- (trimethoxysilyl) propyl group, and the like can be mentioned. The R is₁～R₃The substituent which may be present in the above case is not particularly limited, and examples thereof include an alkyl group, a halogen atom, a hydroxyl group (-OH), a mercapto group (-SH), a cyano group (-CN), and a sulfo group (-SO)₃H) Carboxyl (-COOH), nitro (-NO)₂) And the like. In addition, the substituent present according to circumstances is not related to the substituted R₁～R₃The same is true. For example, at R₁～R₃In the case of alkyl, it is not further substituted byAn alkyl group. Of these, R is preferred₁、R₂And R₃Is hydrogen atom, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, phenyl, vinyl, 3- (triethoxysilyl) propyl or 3- (trimethoxysilylpropyl) group.

In the general formula (1), n is an integer, and the polysilazane having a structure represented by the general formula (1) preferably has a number average molecular weight of 150 to 150000 g/mole.

Among the compounds having a structure represented by the general formula (1), one preferred embodiment is R₁、R₂And R₃Perhydropolysilazanes which are all hydrogen atoms.

Polysilazane is commercially available in the form of a solution obtained by dissolving it in an organic solvent, and the commercially available product can be used as it is as a gas barrier layer-forming coating liquid. Commercially available polysilazane solutions include, for example: AQUAMICA (registered trademark) NN120-10, NN120-20, NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL120-20, NL150A, NP110, NP140, SP140, and polysilazane manufactured by DNF corporation, AZ ELECTRONIC MATERIALS, Inc., and the like.

When polysilazane is used, the content of polysilazane in the gas barrier layer before the modification treatment may be 100 mass% assuming that the total mass of the gas barrier layer is 100 mass%. When the gas barrier layer contains a substance other than polysilazane, the content of polysilazane in the layer is preferably 10 mass% or more and 99 mass% or less, more preferably 40 mass% or more and 95 mass% or less, and particularly preferably 70 mass% or more and 95 mass% or less.

In addition, the coating liquid for forming a gas barrier layer preferably contains an aluminum compound from the viewpoint of improving the heat resistance of the gas barrier layer, and examples of the aluminum compound include trimethoxyaluminum, triethoxyaluminum, and the like, and specific examples of commercially available products include AMD (mono-sec-butyl aluminum di-propionate), ASBD (sec-butyl aluminum), ALCH (ethyl acetoacetate-di-isopropyl aluminum), and the like. The content of the coating liquid for forming a gas barrier layer is preferably 0.1 to 10% by mass, more preferably 1 to 5% by mass.

Further, other examples of polysilazanes ceramized at a low temperature include: a silane oxide-added polysilazane obtained by reacting a polysilazane having a main skeleton containing a unit represented by the general formula (1) with a silane oxide (see, for example, Japanese patent application laid-open No. 5-238827), a glycidol-added polysilazane obtained by reacting with glycidol (see, for example, Japanese patent application laid-open No. 6-122852), and an alcohol-added polysilazane obtained by reacting with an alcohol (see, for example, Japanese patent application laid-open No. 6-240208), a metal carboxylate-added polysilazane obtained by a reaction with a metal carboxylate (see, for example, japanese patent application laid-open No. 6-299118), an acetylacetonate complex-added polysilazane obtained by a reaction with an acetylacetonate complex containing a metal (see, for example, japanese patent application laid-open No. 6-306329), a metal fine particle-added polysilazane obtained by adding metal fine particles (see, for example, japanese patent application laid-open No. 7-196986), and the like.

In the present invention, the gas barrier layer is preferably produced by a wet forming method or an inkjet printing method in the same manner as the solvent permeation preventing layer.

As the wet forming method applicable to the formation of the gas barrier layer, the above-mentioned spin coating method, casting method, screen printing method, die coating method, doctor blade coating method, roll coating method, spray coating method, curtain coating method, LB method (langmuui-Blodgett spray method), dispenser and the like can be cited, and from the viewpoint of easily obtaining a homogeneous thin film and improving productivity, the die coating method, roll coating method, spray coating method and the like are preferable.

Modification of gas barrier layer

The gas barrier layer of the present invention preferably contains polysilazane and a modified product thereof, and can be obtained by, for example, modifying polysilazane in the polysilazane-containing gas barrier layer obtained by the wet formation method. The modification treatment is a reaction of converting a part or all of polysilazane into silicon oxide or silicon oxynitride.

The modification treatment is preferably carried out by vacuum ultraviolet irradiation as exemplified in the modification treatment method of the solvent permeation preventive layer.

The mechanism of the reaction of generating silicon oxynitride from perhydropolysilazane and further generating silicon oxide in the vacuum ultraviolet irradiation step is explained below.

(1) Dehydrogenation and the concomitant formation of Si-N bonds

It is considered that Si-H bonds and N-H bonds in perhydropolysilazanes are easily broken by excitation by vacuum ultraviolet irradiation or the like, and bonding is performed again as Si-N in an inert atmosphere (Si unbonded arms are sometimes formed). I.e. not oxidized but as SiN_yAnd curing. In this case, no cleavage of the polymer backbone occurs. The cleavage of Si-H bond and N-H bond is promoted by the presence of a catalyst and heating. H obtained by cleavage as H₂And discharged out of the membrane.

(2) Formation of Si-O-Si bond by hydrolysis/dehydration condensation

The Si-N bond in perhydropolysilazanes is hydrolyzed by water, the polymer backbone is broken and Si-OH is formed. The two Si-OH groups are subjected to dehydration condensation to form Si-O-Si bonds and are solidified. This is a reaction occurring in the air, but in vacuum ultraviolet irradiation in an inert atmosphere, it is considered that water vapor generated from the base material by the heat of irradiation becomes a main moisture source. When the water content is excessive, Si-OH remaining incompletely condensed by dehydration becomes SiO_2.1～_2.3The composition (2) represents a cured film having a low gas barrier property.

(3) Direct oxidation by singlet oxygen, formation of Si-O-Si bonds

When an appropriate amount of oxygen is present in the atmosphere during vacuum ultraviolet irradiation, singlet oxygen having a very strong oxidizing ability is formed. H, N in perhydropolysilazane is substituted with O to form Si-O-Si bonds and cured. It is thought that bond recombination sometimes occurs due to cleavage of the polymer backbone.

(4) Oxidation accompanying Si-N bond cleavage by vacuum ultraviolet irradiation/excitation

It is considered that the energy of vacuum ultraviolet rays is higher than the bond energy of Si-N in perhydropolysilazane, and therefore the Si-N bond is broken and oxidized to form Si-O-Si bond and Si-O-N bond when oxygen source such as oxygen, ozone, water or the like exists therearound. It is thought that bond recombination sometimes occurs due to cleavage of the polymer backbone.

The composition of the silicon oxynitride in the layer obtained by irradiating the polysilazane-containing layer with vacuum ultraviolet light can be adjusted by appropriately combining the oxidation mechanisms (1) to (4) described above and controlling the oxidation state.

Modification of polysilazane is limited by the ultraviolet intensity of a lamp, irradiation time, temperature conditions at the irradiation time, and the like in usual production, and even if the above-mentioned reactions (1) to (4) occur, it is difficult to convert all of polysilazane in the layer, and therefore, in modification treatment of produced polysilazane, unmodified polysilazane remains in a range of several% in most cases.

In the modification of the gas barrier layer by the vacuum ultraviolet irradiation treatment in the present invention, the conditions of the irradiation of the solvent permeation preventing layer with vacuum ultraviolet rays as described above can be suitably used as the conditions of the illuminance, the irradiation energy, the selection of the light source, the oxygen concentration at the time of irradiation, the heating treatment, and the like.

For example, the modification treatments can be referred to as described in paragraphs "0055" to "0091" of Japanese patent laid-open No. 2012-086394, paragraphs "0049" to "0085" of Japanese patent laid-open No. 2012-006154, and paragraphs "0046" to "0074" of Japanese patent laid-open No. 2011-251460.

[ 5] electronic apparatus

As examples of application of the laminate of the present invention to electronic devices, a touch panel sensor, an organic electroluminescence element, a solar cell having an organic photoelectric conversion element, and an organic thin film transistor will be described.

Preparation of [ 5.1 ] touch Panel sensor

Fig. 2A to D are schematic diagrams showing a manufacturing flow of the touch panel sensor.

(a) Preparation of the substrate (11)

Examples of the substrate used in the touch panel sensor (10) include colorless and transparent glass, and a film or sheet containing a resin. Examples of the resin used for such a base material include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyolefin resins such as Polyethylene (PE), polypropylene (PP), and cyclic polyolefin; a polyamide-based resin; a polycarbonate-series resin; a polystyrene-based resin; a polyvinyl alcohol-based resin; saponified ethylene-vinyl acetate copolymers; polyacrylonitrile-based resin; an acetal resin; a polyimide resin; cellulose ester resins.

Among these resins, a resin selected from the group consisting of polyester resins, polyimide resins, cyclic polyolefin resins, and polycarbonate resins is particularly preferable. These resins may be used alone in 1 kind or in combination of 2 or more kinds.

The thickness of the base material is preferably in the range of 5 to 500 μm in view of stability during production.

(b) Formation of electrode patterns

As for the electrode (12), for example, a transparent conductive film containing Indium Tin Oxide (ITO), silver (Ag), or copper (Cu) is preferably patterned into a predetermined shape to form a metal pattern electrode.

Specifically, the etching solution is preferably used in combination with photolithography. Further, it is also preferably formed by an inkjet printing method.

The line width of the electrode to be formed is preferably 50 μm or less, and particularly preferably 20 μm or less.

The photolithography method applied to the present invention can process a metal thin film layer into a predetermined pattern and can appropriately change the shape of the pattern through the steps of resist coating of a curable resin or the like, preheating, exposure, development (removal of uncured resin), rinsing, etching treatment with an etching solution, and resist stripping.

In the present invention, a conventionally known general photolithography method can be suitably used. For example, as the resist, either a positive type or a negative type resist can be used. In the exposure, a pattern mask having a predetermined pattern is disposed, and then light having a wavelength suitable for the resist to be used, typically ultraviolet rays, electron beams, or the like, is irradiated. After exposure, development is performed with a developer suitable for the resist used. After the development, the development is stopped by a rinse liquid such as water, and the resist pattern is formed by cleaning. Next, the resist pattern obtained by the formation is subjected to pretreatment or post-baking as necessary, and then etched with an etching solution containing an organic solvent to dissolve the solvent permeation preventive layer in the region not protected by the resist and remove the silver thin film electrode. After the etching, the remaining resist is stripped off, thereby obtaining a transparent electrode having a given pattern.

(c) Formation of a smoothing layer

The smoothing layer (13) is a layer formed so as to cover the electrode pattern and smoothed. The smoothing layer can be formed, for example, by applying a coating liquid containing a photosensitive resin and performing a curing treatment. Examples of the photosensitive resin include: a resin composition containing an acrylate compound having a radically reactive unsaturated compound, a resin composition containing an acrylate compound and a mercapto compound having a thiol group, a resin composition in which a polyfunctional acrylate monomer such as epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, polyethylene glycol acrylate, or glycerol methacrylate is dissolved, and the like.

(d) Lamination of laminates

After the smoothing layer (13) is formed, the laminate (1) of the present invention obtained separately is bonded to the smoothing layer by applying pressure or heat to the adhesive layer (2) side.

Through the above operations, a touch panel sensor with a gas barrier layer was manufactured.

Preparation of [ 5.2 ] organic electroluminescent element

When the laminate of the present invention is laminated on a flexible substrate to form a gas barrier base material, the laminate is used for the production of an organic electroluminescent element (hereinafter referred to as an organic EL element), and an organic EL element which is flexible and foldable can be obtained.

In particular, since the laminate of the present invention can be formed into a thin film, an organic EL device having a long life without causing film cracking due to a thick film can be obtained.

Fig. 3A to D are schematic diagrams showing a manufacturing flow of an organic EL device using paper or cloth as a flexible substrate.

(a) Preparation of paper or cloth

The substrate is preferably a substrate that can be used in various applications, such as glass, resin films, and paper or cloth, and that can be stably attached to substrates having various curved surface shapes indoors and outdoors by using a flexible substrate such as resin films, paper, and cloth.

Commercially available paper or cloth (21) can be used, and the material is not particularly limited. The thickness is suitably selected, and is preferably within a range of 100 to 1000. mu.m, and from the viewpoint of weight reduction, is preferably within a range of 100 to 500. mu.m.

(b) Lamination of laminates

The laminate (1) of the present invention obtained separately is adhered to the paper or cloth (21) by applying pressure or heat to the adhesive layer (2) side of the paper or cloth.

(c) Formation of organic EL element

An organic EL element unit (22) is formed on the gas barrier layer (4) of the laminate (1) by vapor deposition or wet formation.

An outline of the organic EL element applicable to the present invention includes, for example: japanese patent laid-open Nos. 2013-157634, 2013-168552, 2013-177361, 2013-187211, 2013-191644, 2013-191804, 2013-225678, 2013-23599994, 243234, 2013-243236, 2013-242366, 2013-243371, 2013-2424242424179, 2014-003249, 2014-003299, 2014-013910, 2014-017493 and 2014-017494.

(d) Sealing of organic EL element unit

The organic EL element unit (22) thus obtained is sealed by an adhesive (23) and a gas barrier film (24) so as to cover the unit.

Through the above operations, an organic EL element using paper or cloth as a substrate is manufactured.

[ 5.3 ] solar cell having organic photoelectric conversion element

In the electronic device of the present invention, the laminate of the present invention is preferably used as a gas barrier layer of an organic photoelectric conversion element.

The photoelectric conversion element and the solar cell will be described below. In the drawings, although the laminate of the present invention is not shown, the entire element is covered with the laminate of the present invention.

Fig. 4 is a cross-sectional view showing an example of a solar cell having a single structure (a structure in which the bulk heterojunction layer is 1 layer) including a bulk heterojunction type organic photoelectric conversion element.

In fig. 4, a bulk heterojunction organic photoelectric conversion element (200) includes a substrate (201) and, laminated on one surface thereof in this order: a transparent electrode (anode 202), a hole transport layer (207), a photoelectric conversion part (204) of a bulk heterojunction layer, an electron transport layer (or also referred to as a buffer layer.208), and a counter electrode (cathode 203).

The substrate (201) holds a transparent electrode (202), a photoelectric conversion unit (204), and a counter electrode (203) which are stacked in this order. In this embodiment, since light to be photoelectrically converted enters from the substrate (201) side, the substrate (201) is preferably a member that transmits the light to be photoelectrically converted, that is, is transparent to the wavelength of the light to be photoelectrically converted. The substrate (201) may be, for example, a glass substrate or a resin substrate. The substrate (201) is not essential, and for example, a transparent electrode (202) and a counter electrode (203) may be formed on both surfaces of a photoelectric conversion part (204) to constitute a hetero-junction organic photoelectric conversion element (200).

The photoelectric conversion unit (204) is a layer that converts light energy into electric energy, and is configured by having a bulk heterojunction layer in which a p-type semiconductor material and an n-type semiconductor material are uniformly mixed. The p-type semiconductor material functions as a relative electron donor (donor), and the n-type semiconductor material functions as a relative electron acceptor (acceptor). Here, the electron donor and the electron acceptor are "the electron donor and the electron acceptor in which electrons move from the electron donor to the electron acceptor when light is absorbed to form a pair of a hole and an electron (charge separated state)" and do not simply supply or receive electrons like an electrode but supply or receive electrons by a photoreaction.

In fig. 4, light incident from the transparent electrode (202) through the substrate (201) is absorbed by the electron acceptor or the electron donor in the bulk heterojunction layer of the photoelectric conversion section (204), and electrons are transferred from the electron donor to the electron acceptor, thereby forming a pair of holes and electrons (charge separated state). The generated charges are transferred to different electrodes through an internal electric boundary, for example, a potential difference between the transparent electrode 202 and the counter electrode 203 when the work functions of the transparent electrode 202 and the counter electrode 203 are different, so that electrons pass between electron acceptors or holes pass between electron donors, and a photocurrent is detected. For example, when the work function of the transparent electrode (202) is larger than that of the counter electrode (203), electrons are transported to the transparent electrode (202), and holes are transported to the counter electrode (203). When the magnitude of the work function is reversed, the electrons and holes are transported in the opposite direction. Further, by applying a potential between the transparent electrode (202) and the counter electrode (203), the direction of transport of electrons and holes can be controlled.

Although not shown in fig. 4, the present invention may further include: a hole blocking layer, an electron injection layer, a hole injection layer, a smoothing layer, or the like.

In addition, in order to further improve the solar light utilization efficiency (photoelectric conversion efficiency), a tandem type configuration (configuration having a plurality of bulk heterojunction layers) in which such photoelectric conversion elements are stacked may be employed.

Examples of materials that can be used in the above-described layer include n-type semiconductor materials and p-type semiconductor materials described in paragraphs 0045 to 0113 of japanese patent application laid-open No. 2015-149483.

The electrodes constituting the organic photoelectric conversion element preferably use the same anode and cathode used in the organic EL element. In this case, in the organic photoelectric conversion element, the positive charges and the negative charges generated in the bulk heterojunction layer are taken out from the transparent electrode and the counter electrode through the p-type organic semiconductor material and the n-type organic semiconductor material, respectively, and the organic photoelectric conversion element functions as a battery. In each electrode, characteristics suitable for a carrier passing through the electrode are required.

In order to enable the organic photoelectric conversion element to more efficiently extract charges generated in the bulk heterojunction layer, it is preferable to provide a hole transport layer/electron blocking layer between the bulk heterojunction layer and the transparent electrode.

Examples of the material constituting these layers include PEDOT, polyaniline and a doped material thereof, such as Clevios manufactured by herraeus corporation, and a cyano compound described in WO 2006/019270.

The organic photoelectric conversion element preferably has an electron transport layer, a hole blocking layer, and a buffer layer formed between the bulk heterojunction layer and the counter electrode, because charges generated in the bulk heterojunction layer can be extracted more efficiently.

The organic photoelectric conversion element may have various optical functional layers in order to receive sunlight more efficiently. As the optically functional layer, for example, there can be provided: a focusing layer such as an antireflection film or a microlens array, a light diffusion layer capable of diffusing light reflected at the counter electrode and making the light enter the bulk heterojunction layer again, and the like.

[ 5.4 ] organic thin film transistor

Fig. 5 is a schematic cross-sectional view showing a structure of an organic thin film transistor. In the electronic device of the present invention, the laminate of the present invention is preferably used as a gas barrier layer of an organic thin film transistor.

Although not shown in the drawings, the entire transistor is covered with the laminate, as in the organic photoelectric conversion element described above.

In fig. 5A, a source electrode (302) and a drain electrode (303) are formed on a support (306) by a metal foil or the like, a charge-transporting thin film (organic semiconductor layer 301) containing 6, 13-bis-triisopropylsilylethynylpentacene which is an organic semiconductor material described in japanese re-table 2009/101862 is formed between both electrodes, an insulating layer (305) is formed thereon, and a gate electrode (304) is further formed thereon to form an electric field effect transistor.

Fig. 5B shows that the organic semiconductor layer (301) is formed by coating the material formed between the electrodes in fig. 5A with a coating method or the like so as to cover the entire surfaces of the electrodes and the support.

Fig. 5C shows that the organic semiconductor layer (301) is first formed on the support (306) by a coating method or the like, and then the source electrode (302), the drain electrode (303), the insulating layer (305), and the gate electrode (304) are formed.

Fig. 5D shows that after a gate electrode (304) is formed on a support (306) by a metal foil or the like, an insulating layer (305) is formed, a source electrode (302) and a drain electrode (303) are formed thereon by a metal foil or the like, and an organic semiconductor layer (301) formed using the light-emitting composition of the present invention is formed between the electrodes.

The configurations shown in fig. 5E and 5F may be adopted.

Examples

The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. In the examples, "parts" or "%" are used, and unless otherwise specified, "parts by mass" or "% by mass" are used.

Example 1

When each of the following liquids was applied to a sheet-like adhesive with a release film (manufactured by 3M) to form a laminate by operations such as film formation, surface modification, and lamination of a gas barrier layer by a spin coating method, the results of observation of the coated surface, light transmittance, evaluation of the adhesive strength of the release film surface, and evaluation of a bending test were performed.

[ preparation of laminate 101 ]

The laminate 101 was prepared by the following procedure.

< adhesive layer >

A sheet-like adhesive (manufactured by 3M) with a release film having an adhesive layer thickness of 25 μ M was used.

< preparation of solvent permeation preventive layer >

As a material of the solvent permeation preventive layer, the following polydimethylsiloxane was used.

UV-PDMS KER-4690: UV-curable polydimethylsiloxane manufactured by shin-Etsu chemical Co

The UV curable resin was spin-coated in a layer thickness of 250nm to form a film on the adhesive layer, and the adhesive layer was irradiated with UV: 365 nm.

(conditions for curing solvent permeation preventive layer)

And (3) performing UV: 365nm, 3J/cm²The irradiation conditions of (3) were set to 1 minute.

[ production of laminate 102 ]

The laminate 102 was prepared in the same manner except that the UV-PDMS KER-4690 described in the preparation of the laminate 101 was diluted with a cyclic siloxane-based solvent (DMCPS: decamethylcyclopentasiloxane) at a mixing mass ratio of PDMS/DMCPS: 1/12.

[ production of laminate 103 ]

The laminate 103 was prepared in the same manner except that the layer thickness of the solvent permeation preventive layer in the preparation of the laminate 101 was changed to 5000 nm.

[ production of laminates 104 and 105 ]

Laminate 104 was prepared in the same manner as described above except that DianalB R85 (available from MITSUBISHI RAYON, Inc., acrylic resin Mw: 280000) was used as the acrylic resin instead of UV-PDMS KER-4690 used in the preparation of laminate 1.

The laminate 105 was produced in the same manner except that a liquid bisphenol a type epoxy resin ("828 EL" manufactured by JAPAN epoxy resin corporation) was used as the epoxy resin instead of the UV-PDMS KER-4690 described in the production of the laminate 1.

[ production of laminates 106 to 108 ]

In the preparation of laminate 1, the UV-PDMS KER-4690: UV-curable polydimethylsiloxane (manufactured by shin-Etsu chemical Co., Ltd.) was spin-coated on the adhesive layer in a thickness of 250nm to form a film of 3J/cm²Irradiation conditions of (1) UV: 365nm, the surface modification treatment described in the following Table I was performed to prepare laminates 106 to 108.

(VUV: vacuum ultraviolet irradiation treatment)

An excimer irradiation device MODEL manufactured by MDCOM (ltd.): MECL-M-1-200

Wavelength: 172nm

Lamp envelope gas: xe (Xe)

Excimer light intensity: 6J/cm²

Distance between sample and light source: 2mm

Stage heating temperature: 80 deg.C

Oxygen concentration in the irradiation apparatus: 0.1% by volume

(flash firing treatment)

Using a xenon flash lamp 2400WS (manufactured by COME T) equipped with a short-wavelength cut-off filter of 250nm or less, the total of irradiation light irradiation energies was 2J/cm in an atmosphere of 0.002% by volume of oxygen and 0.002% by volume of water vapor (0.004% by volume of oxygen-containing substance) for an irradiation time of 2m seconds²The flash firing treatment is performed.

(plasma ion implantation treatment)

The surface of the obtained solvent-permeation-preventing layer was coated at 2J/cm using a plasma ion implantation apparatus (RF power source: manufactured by Nippon electronics Co., Ltd., RF56000, high-voltage pulse power source: Shitakusho Seisakusho, Ltd., PV-3-HSHV-0835)²Plasma ion implantation is performed under the conditions of (1).

< measurement of modified layer thickness >

The depth profile of the solvent permeation preventive layer obtained by the modification treatment was measured to determine the modified layer thickness.

The device comprises the following steps: QuanteraSXM made by ULVAC-PHI

X-ray: mono-colorized Al-Ka

Sputtering ions: ar + (3kV)

As a result, it was found that the carbon content ratio of 0 to 70nm in the surface depth of the solvent permeation preventive layer was 12 at% on average, the carbon content ratio of 70 to 250nm in the surface depth was 30 at% on average, and the surface thickness of the solvent permeation preventive layer was modified to 70 nm. In the present invention, a layer having a lower carbon content than a usual layer is defined as a modified layer. Since the high energy irradiation decomposes and volatilizes the carbon component, a film having a low carbon component is generally considered to be denser.

In addition, in the case of the flash firing treatment and the plasma ion implantation treatment, modification is performed, but the modification is weak as compared with the vacuum ultraviolet treatment.

[ preparation of laminate 109 ]

In the production of the laminate 106, the coating was applied to the solvent permeation preventing layer so that the dry layer thickness of the gas barrier layer using the following PHPS was 250nm, and then the VUV was performed: the laminate 109 was prepared by vacuum ultraviolet irradiation treatment.

< preparation of gas Barrier layer >

The coating solution containing PHPS was prepared by mixing a dibutyl ether solution containing 20 mass% of PHPS (manufactured by AZ ELECTRONIC MATERIALS, NN120-20) and a dibutyl ether solution containing PHPS20 mass% of an amine catalyst (N, N' -tetramethyl-1, 6-diaminohexane (TMDAH)) in a ratio of 4:1 (mass ratio), and further appropriately diluting with dibutyl ether to adjust the dry layer thickness.

[ production of laminates 110 and 111 ]

Laminate 110 was prepared in the same manner as laminate 109 except that a sheet-like adhesive with a release film (3M) having an adhesive layer with a thickness of 5 μ M was used.

In addition, the laminate 111 was prepared in the same manner as in the preparation of the laminate 108 except that the UV-PDMS KER-4690 was diluted with a cyclic siloxane-based solvent (DMCPS: decamethylcyclopentasiloxane) at a mixing mass ratio of PDMS/DMCPS: 1/12.

[ production of laminates 112 and 113 ]

The laminate 112 was prepared in the same manner except that the gas barrier layer obtained by formation was heated at 100 ℃ for 30 minutes using a sol-gel solution described below instead of PHPS used for the gas barrier layer in the preparation of the laminate 109.

< Sol-gel solution containing organic Metal alkoxide >

Titanium tetraisopropoxide (Ti (O)) was prepared in a glove box under a dry nitrogen atmosphere having a water concentration of 1ppm or lessiPr)₄) The solution of 0.1M dehydrated tetrafluoropropanol (exemplified by compound F-1) was bubbled 40mL with air having a humidity of 50% sealed in a glass syringe, and immediately returned to the glove box to obtain a sol-gel solution.

Laminate 113 was produced in the same manner except that the following TE OS solution was used instead of PHPS used for the gas barrier layer in the production of laminate 109.

< TEOS solution >

Tetraethoxysilane (Si (OET) was prepared in a glove box under a dry nitrogen atmosphere having a water concentration of 1ppm or less₄) The dehydrated tetrafluoropropanol solution (0.1M) was bubbled 40mL with air having a humidity of 50% sealed in a glass syringe, and immediately returned to the glove box, and the obtained solution was used as a TEOS solution.

[ production of laminates 114 to 117 (comparative example) ]

In the preparation of the laminate 109, as shown in table I, laminates in which only an adhesive layer (no solvent permeation preventing layer or gas barrier layer) and a gas barrier layer were directly applied to the adhesive layer were prepared, and the laminates 114 to 117 were used as comparative examples.

Evaluation

(1) The observation of the coated surface was carried out,

the coated surface of each sample was observed to evaluate whether it was colorless and transparent or white turbid. In the case of white turbidity, it was shown that the solvent of the upper layer dissolved the lower layer.

(2) Evaluation of light transmittance

The light transmittance was calculated from the absorbance (%) of light having a wavelength of 450nm of each sample. The light absorption was measured by using a spectrophotometer U-4100 manufactured by HITACHI HIGH-TECHNOLOGIES.

From this light transmittance, the light transmittance was evaluated in grades based on the following evaluation criteria. When the light transmittance is high, the transparency of the laminate is high.

5: the light transmittance is more than 95 percent

4: the light transmittance is more than 90% and less than 95%

3: the light transmittance is more than 85% and less than 90%

2: the light transmittance is more than 70% and less than 85%

1: light transmittance of 70% or less

(3) Evaluation of adhesive Strength

Each of the prepared samples was attached to a polyethylene terephthalate film (PET film) having a thickness of 125 μm.

For bonding, the sample was put into a glove box, and the sheet-like adhesive surface from which the release film was removed was bonded to a PET film using a vacuum laminator. At this time, heating was performed at 110 ℃. The sample obtained by adhesion was placed on a heating plate set at 110 ℃ and cured for 30 minutes.

The adhesion of the sample obtained by the bonding was evaluated by the following crosscut method.

< Cross-cut method >

A grid tape test (old JIS K5400) was carried out.

For the test surface, a knife was used to form 11 cuts across and up to the base and to make 100 grids.

Next, the scotch tape was strongly pressed to the mesh portion, the edge of the tape was peeled off at one time at an angle of 45 °, and the state of the mesh between the solvent permeation-preventing layer and the PHPS layer was compared with the standard chart (fig. 6) and evaluated.

(4) Evaluation of appearance after bending

The prepared sample was kept at a diameter of the winding

While in the state of being on the column, the reaction solution was held at 25 ℃ and 50% RH for 1000 hours. Then, with respect to this sample, the appearance of the element after 1000 hours of holding was visually observed, and evaluation of cracks was performed based on the following criteria. Among linear defects having a thickness of 0.5 μm or more, those having a length of 1000 μm or more were evaluated as cracks.

O: light emitting area 100cm²Less than 5 cracks in the steel

And (delta): light emitting area 100cm²The number of cracks in the steel sheet is 5 or more and less than 50

X: light emitting area 100cm²The number of cracks in the steel sheet is 50 or more

The composition and evaluation results of the laminate are shown in table I.

[ Table 1]

TABLE I

As is apparent from table I, by first applying a solvent permeation preventive layer on the adhesive layer, the gas barrier material can be applied from the upper layer to form a film without damaging the adhesive itself.

It is also known that the solvent permeation preventive layer on the adhesive layer particularly preferably contains a silicone resin.

It is known that the modification method of the solvent permeation preventive layer is preferably vacuum ultraviolet ray treatment (VUV: 172 nm).

It is found that, compared to the conventional adhesive-only configuration, the laminate of the present invention including the adhesive/solvent permeation preventing layer/gas barrier layer can have a significantly reduced film thickness and thus improved bendability.

Example 2

Each of the coating liquids for the solvent permeation preventive layer used in example 1 was spin-coated on a silicon wafer at a rate of 3J/cm²Irradiation conditions of (1) UV: 365 nm. Next, each surface treatment described in table II was performed, and these were set as measurement samples.

Evaluation

(4) Determination of contact Angle

In the measurement of the contact angle of pure water on the surface of the solvent permeation preventive layer, 1. mu.L of pure water was dropped using a contact angle meter (product name DropMaster DM100, manufactured by Kyowa Kagaku K.K.) under an atmosphere of 23 ℃ and 55% RH based on JIS-R3257, and the contact angle after 1 minute was measured. In the measurement, 10 spots were measured at equal intervals in the width direction of the organic thin film, and the maximum value and the minimum value were removed to obtain an average value as a contact angle.

The results are shown in Table II.

[ Table 2]

TABLE II

As is clear from Table II, the treatment by vacuum ultraviolet treatment (VUV: 172nm) is most effective for improving the wettability of the film surface, that is, for improving the adhesion to the upper layer.

Example 3

Each of the solvent permeation preventive layer coating liquids used in example 1 was spin-coated as a solvent permeation preventive layer onto a silicon wafer at 3J/cm²Irradiation conditions of (1) UV: 365 nm. Next, each surface treatment described in Table III was performed, and then a coating liquid containing PHPS was spin-coated on the solvent-repellent layer, dried at 80 ℃ for 1 minute by a hot plate, and applied at 6J/cm²The irradiation conditions of (2) were vacuum ultraviolet ray treatment (VUV: 172nm), and the obtained sample was designated as a measurement sample.

Evaluation

(5) Evaluation of adhesion

The state of the mesh between the solvent permeation preventing layer and the PHPS layer was compared with a standard chart (fig. 6) and adhesion was evaluated by using the cross-cut mesh tape test performed in example 1.

The results are shown in Table III.

[ Table 3]

TABLE III

From these results, it was found that the surface modification treatment by vacuum ultraviolet ray treatment (VUV: 172nm) of the solvent permeation preventive layer is most effective for improving the adhesion between the solvent permeation preventive layer and the PHPS layer.

Example 4

< preparation of organic EL element for evaluation >

(preparation of substrate)

First, a gas barrier layer of an inorganic substance containing SiOx was formed so as to have a layer thickness of 500nm using an atmospheric pressure plasma discharge treatment apparatus having the structure described in jp 2004-68143 a on the entire surface of a polyethylene naphthalate FILM (manufactured by FILM solvent corporation) on which an anode side was formed. Thus, a film having an oxygen permeability of 0.001 mL/(m)²24h atom) or less, water vapor transmission rate of 0.001 g/(m)²24h) or less.

(formation of Anode)

ITO (indium tin oxide) having a thickness of 120nm was formed on the substrate by a sputtering method, and patterned by a photolithography method to form an anode. The pattern is a pattern having an area of a light-emitting region of 5cm × 5 cm.

(formation of hole injection layer)

The substrate on which the anode was formed was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes. Then, on the substrate on which the anode was formed, a 2 mass% solution obtained by diluting a dispersion of poly (3, 4-ethylenedioxythiophene)/polystyrene sulfonate (PEDOT/PSS) prepared in the same manner as in example 16 of Japanese patent No. 4509787 was applied by inkjet printing, and dried at 80 ℃ for 5 minutes to form a hole injection layer having a layer thickness of 40 nm.

(formation of hole transport layer)

Next, the substrate on which the hole injection layer was formed was transferred to a nitrogen atmosphere using nitrogen gas (G1 grade), coated by an inkjet printing method using a hole transport layer forming coating liquid having the following composition, and dried at 150 ℃ for 30 minutes to form a hole transport layer having a layer thickness of 30 nm.

Coating liquid for forming hole transport layer

Hole-transporting material HT-3 (weight-average molecular weight Mw 80000)

10 parts by mass

3000 parts by mass of p-xylene

(formation of luminescent layer)

Next, the substrate having the hole transporting layer formed thereon was coated by an ink jet method using a coating liquid for forming a light-emitting layer having the following composition, and dried at 130 ℃ for 30 minutes to form a light-emitting layer having a layer thickness of 50 nm.

Coating liquid for forming light-emitting layer

(formation of Barrier layer)

Next, the substrate on which the light-emitting layer was formed was coated by an ink jet method using a coating liquid for forming a barrier layer having the following composition, and dried at 80 ℃ for 30 minutes to form a barrier layer having a layer thickness of 10 nm.

Coating liquid for forming barrier layer

HB-42 parts by mass

1500 parts by mass of isopropyl alcohol (IPA)

500 parts by mass of 2,2,3,3,4,4,5, 5-octafluoro-1-pentanol

(formation of an electron transport layer)

Next, the substrate on which the barrier layer was formed was coated by an inkjet printing method using a coating liquid for forming an electron transport layer having the following composition, and dried at 80 ℃ for 30 minutes to form an electron transport layer having a layer thickness of 30 nm.

Coating liquid for forming electron transport layer

ET-16 parts by mass

2000 parts by mass of 2,2,3, 3-tetrafluoro-1-propanol

(formation of Electron injection layer and cathode)

Next, the substrate was mounted to a vacuum evaporation apparatus without being exposed to air. Further, a molybdenum resistance heating plate containing sodium fluoride and potassium fluoride was attached to a vacuum evaporation apparatus, and the pressure in the vacuum chamber was reduced to 4X 10^-5Pa. Then, the plate was heated while being energized, and sodium fluoride was deposited on the electron transport layer at 0.02 nm/sec to form a thin film having a thickness of 1 nm. Similarly, potassium fluoride was deposited on the sodium fluoride thin film at 0.02 nm/sec to form an electron injection layer having a layer thickness of 1.5 nm.

Next, aluminum was evaporated and a cathode having a thickness of 100nm was formed.

Then, the release film of the laminate prepared in the same manner as the laminate described in example 1 was peeled off and bonded to an organic EL device, thereby preparing organic EL devices 401 to 406. The organic EL element 407 is bonded only with the adhesive layer.

For bonding, the sample was put into a glove box, and the sheet-like adhesive surface from which the release film was removed was bonded to the cathode using a vacuum laminator. At this time, heating was performed at 110 ℃. The sample obtained by adhesion was placed on a heating plate set at 110 ℃ and cured for 30 minutes.

The compounds used are shown below.

[ chemical formula 13]

Evaluation

(6) Resistance to dark spots

The resulting mixture was left at 60 ℃ and 90% RH for 1 week, and then the emission state was observed to evaluate the gas barrier properties. Specifically, a part of the light emitting part of the organic EL element was enlarged and photographed by an optical microscope (MS-804, manufactured by MORTEX corporation, lens MP-ZE25-200) at a magnification of 100. Next, the captured image was divided into 2mm squares, and the presence or absence of dark spots was observed for each image. From the observation results, the ratio of the area of dark spot generation to the light emission area was obtained, and the dark spot resistance was evaluated based on the following criteria.

5: no occurrence of dark spots was observed

4: the generation area of dark spots is more than 0.1% and less than 1.0%

3: the generation area of dark spots is more than 1.0% and less than 3.0%

2: the generation area of dark spots is more than 3.0% and less than 6.0%

1: the generation area of dark spots is more than 6.0 percent

The results are shown in Table IV.

[ Table 4]

TABLE IV

The adhesive layer/solvent permeation preventing layer/gas barrier layer structure can be used as a sealing film for an organic EL element. Further, it is found that the sealing property of the organic EL element can be improved by increasing the number of laminated gas barrier layers.

Example 5

A laminate prepared in the same manner as laminate 401 of example 4 was bonded to a polyester felt having a thickness of 1mm, and the felt was used as a base material for an organic EL element according to the flow shown in fig. 3A to D.

Next, the organic EL element unit (anode-to-cathode configuration) of example 4 was formed on the gas barrier layer of the laminate.

Coating UV-PDMS KER-4690 on the cathode of the organic EL element unit by ink-jet printing method to form a film of 3J/cm²Irradiation conditions of (1) UV: 365nm at 1.8J/cm²Vacuum ultraviolet treatment (VUV: 172nm) was carried out under the irradiation conditions of (1). Then, the coating liquid containing PHPS was applied to a solvent-repellent layer by an ink-jet printing method to form a film, which was heated at 80 ℃ for 1 minute and then applied at 6JJ/cm²Vacuum ultraviolet treatment (VUV: 172nm) was carried out under the irradiation conditions of (1). Then, the following gas barrier film was laminated.

(preparation of gas Barrier film)

An atmospheric pressure plasma discharge treatment apparatus having the structure described in jp 2004-68143 a was used to form a gas barrier layer of an inorganic substance containing SiOx so that the layer thickness becomes 500nm over the entire surface of a polyethylene naphthalate FILM (manufactured by FILM solvent corporation). Thus, a film having an oxygen permeability of 0.001 mL/(m)²24 h. atm) or less, and a water vapor transmission rate of 0.001 g/(m)²24h) or less. On one side of the gas barrier film, a thermosetting liquid adhesive (epoxy resin) having a thickness of 25 μm was used as a sealantAnd a sealing resin layer. The gas barrier film provided with the sealing resin layer is stacked on the organic EL element unit and sealed. At this time, the sealing resin layer forming surface of the gas barrier film and the sealing surface side of the organic EL element are continuously overlapped so that the end portions of the extraction portions of the anode and the cathode are protruded to the outside.

The organic EL device produced by the above method emits light in the same manner as an organic EL device produced on an ordinary glass substrate. In general, when an organic EL element layer or a resin layer is directly printed on a felt cloth or the like, liquid penetrates the cloth and cannot be laminated. However, since the fabric to which the laminate of the present invention is bonded can be used to produce an organic EL element which emits light as usual, it has been confirmed that a gas barrier substrate can be produced using a fabric, paper, or the like.

Example 6

< preparation of touch Panel Module >

As the flexible substrate having a gas barrier layer, a FILM of polyethylene naphthalate (manufactured by Diman FILM SOLUTION Co., Ltd.) having a thickness of 100 μm and made of SiO was used₂A film obtained by film formation with a thickness of 300nm by a plasma CVD method was formed thereon with an ITO film by a sputtering method so as to have a thickness of 20nm, and a 1 st electrode pattern in the X direction was formed by etching.

Next, as an insulating layer disposed between the electrode patterns, SiO was used₂The film was formed using a sputtering method so as to have a thickness of 200nm, and thereon, the film was formed with an ITO film by sputtering so as to have a thickness of 20nm, and the 2 nd electrode pattern was formed in the Y direction by etching. Further, SiO is used as an insulating layer thereon₂The film was formed so as to have a thickness of 200nm by a sputtering method.

The Ag paste was coated and sintered onto the X-direction and Y-direction electrode patterns of the obtained ITO, respectively, and the control circuit was connected by the prepared wires.

Next, the laminate prepared under the conditions of the laminate 401 of example 4 was bonded to the 2 nd electrode pattern via an adhesive layer, to prepare a touch panel module.

The liquid crystal display device including the prepared touch panel module was subjected to temperature change from-20 ℃ to 80 ℃ 200 times in cycles at intervals of 30 minutes in an environment with a relative humidity of 50% RH. The operation of the touch panel module of the liquid crystal display device taken out was checked, and it was found that the operation was possible without any particular problem and the durability was excellent.

In addition, the prepared sample was kept wound around a diameter

While in the state of being on the column, the reaction solution was held at 25 ℃ and 50% RH for 1000 hours. Then, with respect to this sample, the appearance of the device after holding for 1000 hours was visually observed, and whether or not cracks occurred and the operation was confirmed were evaluated, and as a result, the occurrence of cracks was not found, and the operation was normal, and the touch panel module including the laminate of the present invention was excellent in flexibility.

Industrial applicability

The laminate of the present invention can be made thin, prevents film cracking, is easily adapted to flexibility and foldability of electronic devices, and further has gas barrier properties for improving optical characteristics, and therefore, examples of applications of the laminate to electronic devices include touch panel sensors, organic electroluminescent elements, solar cells having organic photoelectric conversion elements, and organic thin film transistors.

Description of the symbols

1 laminated body

2 adhesive layer

3 solvent barrier layer

4 gas barrier layer

5 modified layer

6 organic metal oxide layer

7 diaphragm

10 touch panel sensor

11 substrate

12 electrodes

13 smoothing layer

20 organic EL element

21 paper or cloth

22 organic EL element unit

23 adhesive

24 gas barrier film

200-body heterojunction type organic photoelectric conversion element

201 substrate

202 transparent electrode (Anode)

203 antipode (cathode)

204 photoelectric conversion part (bulk heterojunction layer)

205 charge recombination layer

206 nd 2 photoelectric conversion part

207 hole transport layer

208 electron transport layer

209 st photoelectric conversion part

301 organic semiconductor layer

302 source electrode

303 drain electrode

304 gate electrode

305 insulating layer

306 support body

Claims

the gas barrier layer contains an inorganic material, and,

2. The laminate according to claim 1, wherein,

3. Laminate according to claim 1 or claim 2, wherein,

4. The laminate according to any one of claims 1 to 3,

the solvent permeation preventive layer contains a silicone-based resin.

5. The laminate according to any one of claims 1 to 4,

6. The laminate according to claim 5, wherein,

7. Laminate according to claim 5 or claim 6, wherein,

the thickness of the modified layer is within the range of 1-70 nm.

8. The laminate according to any one of claims 1 to 7,

the gas barrier layer contains polysilazane and a modified product thereof.

9. The laminate according to any one of claims 1 to 8,

r- [ M (OR) of the general formula (A)₁)_y(O-)_x-y]_n-R

Wherein R represents a hydrogen atom, an alkyl group having 1 OR more carbon atoms, an alkenyl group, an aryl group, a cycloalkyl group, an acyl group, an alkoxy group OR a heterocyclic group, wherein R may contain a fluorine atom as a substituent, M represents a metal atom, OR₁Represents a fluoroalkoxy group, x represents the valence of the metal atom, y represents any integer between 1 and x, and n representsThe degree of polycondensation.

10. The laminate according to claim 9, wherein,

11. Laminate according to claim 9 or claim 10, wherein,

12. The laminate according to any one of claims 1 to 11,

13. The laminate according to any one of claims 1 to 11,

a peelable film is disposed on the side of the adhesive layer opposite to the solvent-resistant layer, and

an adhesive layer is further disposed on the gas barrier layer on the side opposite to the solvent permeation preventive layer.

a step of applying a photo-or thermosetting resin to the surface of the adhesive layer to form a solvent permeation preventing layer containing the resin; and

15. The method for producing a laminate according to claim 14, further comprising, after the step of forming the solvent permeation preventive layer:

16. The method for producing a laminate according to claim 14, further comprising, after the step of forming the solvent permeation preventive layer:

17. An electronic device is provided with:

the laminate as claimed in any one of claims 1 to 13.