JP7080216B2 - Gas barrier adhesive film, electronic members and optical members - Google Patents

Description

The present invention relates to a gas barrier adhesive film having excellent antistatic properties, and an electronic member and an optical member provided with a gas barrier layer and an adhesive resin layer derived from the gas barrier adhesive film.

In recent years, organic EL elements have been attracting attention as light emitting elements capable of high-luminance light emission by low-voltage direct current drive.
However, the organic EL element has a problem that the light emission characteristics such as the light emission brightness, the light emission efficiency, and the light emission uniformity tend to deteriorate with the passage of time.
It is conceivable that oxygen, moisture, or the like infiltrate the inside of the organic EL element to deteriorate the electrode and the organic layer as a cause of the problem of deterioration of the light emitting characteristics.
Then, as a method for dealing with this problem, a method using a sealing material has been proposed.
For example, in Patent Document 1, a gas barrier film having a barrier layer containing an organic region and an inorganic region on a base film and having an outermost surface on the side where the organic region is provided is an adhesive layer is used as a sealing material. The sealing method of the display element to be used is described.

Further, Patent Document 2 describes a laminated film having a layer structure of a release film / adhesive layer / gas barrier layer / release film.

JP-A-2010-006039 (US20090061223A1) WO2013 / 018602 (US2014 / 0178622A1)

When a laminated film having a release film as described in Patent Document 2 is used, the release film is peeled off at a predetermined stage.
However, since the film having the gas barrier layer tends to be charged, the gas barrier adhesive film after the release film is peeled off is charged, which adversely affects the organic EL element or causes the gas barrier adhesive film to bend. It sometimes interfered with the pasting work.
Therefore, there has been a demand for a gas barrier adhesive film having excellent antistatic properties.

The present invention has been made in view of the above circumstances, and provides a gas barrier adhesive film having excellent antistatic properties, and an electronic member and an optical member provided with a gas barrier layer and an adhesive resin layer derived from the gas barrier adhesive film. The purpose is to do.

In order to solve the above problems, the present inventors have a gas barrier unit made of a protective film / gas barrier layer and an adhesive unit made of an adhesive resin layer / release film, and the adhesive unit and the gas barrier unit However, the adhesive resin layer of the adhesive unit and the gas barrier layer of the gas barrier unit are laminated so as to face each other, directly or via another layer, and the protective film and the release film are respectively. We have diligently studied the gas barrier adhesive film that constitutes the outermost layer.
As a result, by lowering the surface resistivity of the specific surfaces of the protective film and the release film (to a specific value or less), the antistatic property is excellent, and the work when attaching to the object can be efficiently performed. We have found that a gas barrier adhesive film can be obtained, and have completed the present invention.

Thus, according to the present invention, the following gas barrier adhesive films [1] to [6], and the electronic member and the optical member of (7) are provided.

[1] It has a gas barrier unit made of a protective film / gas barrier layer and an adhesive unit made of an adhesive resin layer / release film, and the adhesive resin layer is directly on the gas barrier layer or another layer. The protective film and the release film are gas barrier adhesive films each constituting the outermost layer, and the surface resistance of the surface of the protective film on the gas barrier layer side is 5.0 ×. A gas barrier adhesive film having a surface resistance of 10 ¹¹ Ω / □ or less and having a surface resistance of at least one of the surfaces of the release film of 5.0 × 10 ¹¹ Ω / □ or less.
[2] The gas barrier adhesive film according to [1], wherein the protective film is a laminated film (α) having a base film (α) and an antistatic pressure-sensitive adhesive partial layer.
[3] The gas barrier adhesive film according to [1] or [2], wherein the gas barrier layer is made of a laminated film (β) having a base film (β) and a gas barrier partial layer.
[4] The gas barrier adhesive film according to any one of [1] to [3], wherein the adhesive resin contained in the adhesive resin layer is a polyolefin-based adhesive resin.
[5] The release film is a laminated film (γ) having a base film (γ), an antistatic partial layer, and a peelable partial layer, and the peelable partial layer constitutes one of the outermost layers. , The gas barrier adhesive film according to any one of [1] to [4].
[6] The gas barrier adhesive film according to any one of [1] to [5], which is an adhesive film for an electronic member or an optical member.
[7] An electronic member or an optical member provided with a gas barrier layer and an adhesive resin layer derived from the gas barrier adhesive film according to any one of [1] to [6] above.

According to the present invention, there is provided a gas barrier adhesive film having excellent antistatic properties, and an electronic member and an optical member provided with a gas barrier layer and an adhesive resin layer derived from the gas barrier adhesive film.

It is a schematic diagram which shows the layer structure of the gas barrier adhesive film of this invention. It is a schematic diagram which shows the layer structure of the gas barrier adhesive film of this invention. It is a schematic diagram which shows the layer structure of the release film (1)-(4) obtained in Production Examples 7-10. It is a schematic diagram which shows the layer structure of the protective film (1)-(4) with a release film obtained in Production Examples 11-14. It is a schematic diagram which shows the layer structure of the gas barrier adhesive film (1), (2) obtained in Examples 1 and 2. It is a schematic diagram which shows the layer structure of the gas barrier adhesive film (3), (4) obtained in Examples 3 and 4. It is a schematic diagram which shows the layer structure of the gas barrier adhesive film (5), (6) obtained in Examples 5 and 6. It is a schematic diagram which shows the layer structure of the gas barrier adhesive film (7), (8) obtained in Comparative Examples 1 and 2. It is a schematic diagram which shows the layer structure of the gas barrier adhesive film (9), (10) obtained in the comparative examples 3 and 4.

Hereinafter, the present invention will be described in detail by dividing it into 1) a gas barrier adhesive film, and 2) an electronic member and an optical member.

1) Gas barrier adhesive film The gas barrier adhesive film of the present invention has a gas barrier unit made of a protective film / gas barrier layer and an adhesive unit made of an adhesive resin layer / release film, and the adhesive resin layer is formed. , The protective film and the release film are gas barrier adhesive films each constituting the outermost layer, which are laminated directly on the gas barrier layer or via other layers, and the protective film is on the gas barrier layer side. The surface resistance of the surface of the release film is 5.0 × 10 ¹¹ Ω / □ or less, and the surface resistance of at least one of the surfaces of the release film is 5.0 × 10 ¹¹ Ω / □ or less. It is characterized by that.
In addition, in this specification, "film" includes not only strip-shaped ones but also long-shaped (strip-shaped) ones.
The "long shape" means a film having a length of at least about 5 times or more with respect to the width direction of the film, preferably having a length of 10 times or more, and specifically a roll shape. A shape that has a length that allows it to be wound around and stored or transported.

When the protective film, gas barrier layer, adhesive resin layer, and release film constituting the gas barrier adhesive film of the present invention have a multilayer structure, the protective film, the gas barrier layer, the adhesive resin layer, and the layer constituting the release film are provided. When expressed, it is sometimes referred to as a "partial layer."

〔Protective film〕
The protective film in the gas barrier unit is a kind of release film, which is a film for protecting the gas barrier layer during transportation and storage of the gas barrier adhesive film, and is finally peeled off.

The surface resistance of the surface of the protective film on the gas barrier layer side (the surface in contact with the gas barrier layer in the gas barrier adhesive film; hereinafter referred to as "surface (A)") is 5.0 × 10 ¹¹ Ω /. It is □ or less, preferably 1.0 × 10 ⁶ Ω / □ or more and 5.0 × 10 ¹¹ Ω / □ or less. By setting the surface resistivity of the surface (A) to 5.0 × 10 ¹¹ Ω / □ or less, the amount of charge on the surface of the gas barrier layer can be reduced after the protective film is peeled off.
Surface resistivity can be measured by the method described in the Examples (same below).
In addition, "Ω / □" (Ohm Per Square) is the resistance value per unit area (the same applies below).

The surface resistance of the other surface of the protective film (the surface exposed to the outside in the gas barrier adhesive film; hereinafter referred to as "surface (B)") is 1.0 x ¹⁰⁶ Ω / □. More than 5.0 × 10 ¹¹ Ω / □ or less is preferable, and 1.0 × 10 ⁶ Ω / □ or more and 5.0 × 10 ¹⁰ Ω / □ or less are more preferable.
The gas barrier adhesive film having a surface resistance of 1.0 × 10 ⁶ Ω / □ or more and 5.0 × 10 ¹¹ Ω / □ or less on the surface (B) may be used when a plurality of gas barrier adhesive films are stacked. When it is wound in a roll shape, the gas barrier adhesive films can be easily peeled off from each other, so that the workability is excellent.

The thickness of the protective film is usually 1 to 300 μm, preferably 10 to 200 μm, and more preferably 20 to 100 μm.
The layer structure of the protective film is not particularly limited. The protective film may have a single-layer structure or may have a multi-layer structure.
Since it is easy to obtain a protective film having the desired characteristics, the protective film having a multilayer structure is preferable.

As the protective film having a multilayer structure, a laminated film having a base film (hereinafter, the base film constituting the protective film is referred to as "base film (α)") and an antistatic pressure-sensitive adhesive partial layer ( Hereinafter, this laminated film is referred to as “laminated film (α)”).

The base film (α) is a paper base material such as glassin paper, coated paper, or high-quality paper; a laminated paper obtained by laminating a thermoplastic resin such as polyethylene or polypropylene on these paper base materials; and cellulose on the above paper base material. , Substrate subjected to sealing treatment with starch, polyvinyl alcohol, acrylic-styrene resin and the like; resin film; and the like.
Among these, a resin film is preferable because it is easy to handle.

Resin components of the resin film include polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polysulfone, polyethersulfone, polyphenylene sulfide, acrylic resin, and cycloolefin polymer. , Aromatic polymers and the like.
These resin components can be used alone or in combination of two or more.

The thickness of the base film (α) is not particularly limited. The thickness of the base film (α) is usually 300 μm or less, preferably 10 to 200 μm.
The base film (α) may or may not contain an antistatic agent, but a film containing an antistatic agent is preferable. Since the base film (α) contains an antistatic agent, it becomes easy to obtain a protective film having a low surface resistivity of the surface (B).

The antistatic agent is not particularly limited as long as it can impart antistatic properties to the base film (α).
Examples of the antistatic agent include an ionic conductive agent, an ionic liquid, a surfactant, a conductive polymer and the like.

Examples of the ionic conductive agent include an ionic conductive agent containing an alkali metal salt and a polyether compound having an alkylene oxide chain.
Alkali metal salts include cations such as Li ⁺ , Na ⁺ , K ⁺ , ^Cl- , Br-, I- ^{, BF4- ,} _PF6- ^, SCN- ^, ClO _4- ^, CF ₃ SO _{3- ,} ⁽ Examples thereof include metal salts composed of anions such as CF ₃ SO ₂ ) N ⁻ and (CF ₃ SO ₂ ) C ⁻ . Among these, lithium salts such as LiBr, LiI, LiBF ₄ , LiPF ₆ , LiSCN, LiClO ₄ , LiCF ₃ SO ₃ , Li (CF ₃ SO ₂ ) N, and Li (CF ₃ SO ₂ ) C are preferable.

Examples of the polyether compound include a polyether polyol and a polyester polyol. The polyether compound is preferably a liquid at 25 ° C.
Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol and derivatives thereof.

Examples of the polyester polyol include a reaction product of an acid component and a glycol component or a polyol component, and a ring-opening polymerization reaction product of lactones.
Examples of the acid component include terephthalic acid, adipic acid, azelaic acid, sebatic acid, phthalic anhydride, isophthalic acid, trimellitic acid and the like.
Glycol components include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,6-hexaneglycol, 3-methyl-1,5-pentanediol, 3,3'-dimethylol heptane, polyoxyethylene glycol, and polyoxy. Examples thereof include propylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol and the like.
Examples of the polyol component include glycerin, trimethylolpropane, pentaerythritol and the like.
Examples of the lactones include polycaprolactone, poly (β-methyl-γ-valerolactone), polyvalerolactone and the like.

Further, as the polyether compound, an organopolysiloxane having an alkylene oxide chain in the side chain disclosed in JP-A-6-313807 can be used.

The ionic liquid refers to an ionic compound that is liquid at 25 ° C.
Examples of the ionic liquid include nitrogen-containing onium salt, sulfur-containing onium salt and phosphorus-containing onium salt.

Examples of the cation constituting the ionic liquid include a cation having a heterocycle in the molecule and a cation having no heterocycle in the molecule.
The cation having a hetero ring in the molecule includes a cation having one nitrogen atom in the hetero ring (hereinafter, may be referred to as "cation (A)") and a cation having two nitrogen atoms in the hetero ring (hereinafter, may be referred to as "cation (A)"). However, the two nitrogen atoms are not adjacent to each other. Hereinafter, they may be referred to as "cation (B)"), a cation having two nitrogen atoms in the heterocycle (however, the two nitrogen atoms are adjacent to each other). Hereinafter, it may be referred to as "cation (C)".)

Examples of the cation (A) include a pyridinium cation, a piperidinium cation, a pyrrolidinium cation, a cation having a pyrroline skeleton, and a cation having a pyrrole skeleton. Specific examples of these include 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-hexyl. -3-Methylpyridinium cation, 1-butyl-3,4-dimethylpyridinium cation, 1,1-dimethylpyrridinium cation, 1-ethyl-1-methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidiium Examples thereof include a nium cation, a 2-methyl-1-pyrrolin cation, a 1-ethyl-2-phenylindole cation, a 1,2-dimethylindole cation and a 1-ethylcarbazole cation.

Examples of the cation (B) include an imidazolium cation, a tetrahydropyrimidinium cation, and a dihydropyrimidinium cation. Specific examples of these include 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-butyl-3-methylimidazolium cation, 1-to. Xyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-dodecyl-3-methylimidazolium cation, 1-tetradecyl-3-methylimidazolium cation Rium cation, 1,2-dimethyl-3-propylimidazolium cation, 1-ethyl-2,3-dimethylimidazolium cation, 1-butyl-2,3-dimethylimidazolium cation, 1-hexyl-2,3 -Dimethylimidazolium cations, 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium cations, 1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium cations, 1, 2,3,4-Tetramethyl-1,4,5,6-Tetrahydropyrimidinium cation, 1,2,3,5-Tetramethyl-1,4,5,6-Tetrahydropyrimidinium cation, 1, 3-Dimethyl-1,4-dihydropyrimidinium cation, 1,3-dimethyl-1,6-dihydropyrimidinium cation, 1,2,3-trimethyl-1,4-dihydropyrimidinium cation, 1, 2,3-trimethyl-1,6-dihydropyrimidinium cation, 1,2,3,4-tetramethyl-1,4-dihydropyrimidinium cation and 1,2,3,4-tetramethyl-1, 6-Dihydropyrimidinium cations and the like can be mentioned.

Examples of the cation (C) include pyrazolium cations and pyrazolinium cations. Specific examples of these include 1-methylpyrazolium cation, 3-methylpyrazolium cation, 1-ethyl-2-methylpyrazolinium cation and the like.

Examples of the cation having no heterocycle in the molecule include a tetraalkylammonium cation, a trialkylsulfonium cation, a tetraalkylphosphonium cation, and a cation in which a part of the above alkyl group is replaced with an alkenyl group, an alkoxyl group, an epoxy group, or the like. Can be mentioned.
Specific examples of these include tetramethylammonium cations, tetraethylammonium cations, tetrabutylammonium cations, and tetrahexylammonium cations.
Trimethylheptylammonium cation, trimethyldecylammonium cation, triethylmethylammonium cation, triethylpropylammonium cation, triethylpentylammonium cation, triethylheptylammonium cation, tributylethylammonium cation, trioctylmethylammonium cation,

N, N-dimethyl-N, N-dipropylammonium cation, N, N-dimethyl-N, N-dihexylammonium cation, N, N-dipropyl-N, N-dihexylammonium cation,
N, N-dimethyl-N-ethyl-N-propylammonary cation, N, N-dimethyl-N-ethyl-N-butylammonium cation, N, N-dimethyl-N-ethyl-N-pentylammonium cation, N, N-dimethyl-N-ethyl-N-hexylammonary cation, N, N-dimethyl-N-ethyl-N-heptylammonium cation, N, N-dimethyl-N-ethyl-N-nonylammonium cation, N, N- Dimethyl-N-propyl-N-butylammonary cations, N, N-dimethyl-N-propyl-N-pentylammonium cations, N, N-dimethyl-N-propyl-N-hexylammonium cations, N, N-dimethyl- N-propyl-N-heptylammonium cations, N, N-dimethyl-N-butyl-N-hexylammonary cations, N, N-dimethyl-N-butyl-N-heptylammonium cations, N, N-dimethyl-N- Pentyl-N-hexylammonium cation, N, N-diethyl-N-methyl-N-propylammonium cation, N, N-diethyl-N-methyl-N-pentylammonium cation, N, N-diethyl-N-methyl- N-Heptylammonium cation, N, N-diethyl-N-propyl-N-pentylammonium cation, N, N-dipropyl-N-methyl-N-ethylammonary cation, N, N-dipropyl-N-methyl-N- Pentylammonium cations, N, N-dipropyl-N-butyl-N-hexylammonium cations, N, N-dibutyl-N-methyl-N-pentylammonium cations, N, N-dibutyl-N-methyl-N-hexylammonium Cationic,
N-methyl-N-ethyl-N-propyl-N-pentylammonium cation,
Ammonium ions such as diallyldimethylammonium cations, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium cations, glycidyltrimethylammonium cations;

Trimethylsulfonium cation, triethylsulfonium cation, tributylsulfonium cation, trihexylsulfonium cation,
Sulfonium cations such as dimethyldecylsulfonium cations, diethylmethylsulfonium cations, dibutylethylsulfonium cations;

Tetramethylphosphonium cation, tetraethylphosphonium cation, tetrabutylphosphonium cation, tetrahexylphosphonium cation,
Phosphonium cations such as trimethyldecylphosphonium cation, triethylmethylphosphonium cation, tributylethylphosphonium cation; and the like can be mentioned.

The anion constituting the ionic liquid is not particularly limited as long as the salt becomes an ionic liquid. Anions include ^Cl- , Br- ^, I- ^, AlCl _4- ^, Al ₂ Cl _7- ^, BF _4- ^, PF _6- ^, ClO _4- ^, NO _3- ^, CH ₃ COO- ^, CF ₃ COO- ^, CH. ₃ SO _3- ^, CF ₃ SO _3- ^, (CF ₃ SO ₂ ) ₂ N- ^, (CF ₃ SO ₂ ) ₃ C- ^, AsF _6- ^, SbF _6- ^, NbF _6- ^, TaF _6- ^, F (HF) ) _N- ^, (CN) ₂ N- ^, C ₄ F ₉ SO _3- ^, (C ₂ F ₅ SO ₂ ) ₂ N- ^, C ₃ F ₇ COO- ^, (CF ₃ SO ₂ ) (CF ₃ CO) N ^-Etc .

As ionic liquids, 1-butylpyridinium tetrafluoroborate, 1-butylpyridinium hexafluorophosphate, 1-butyl-3-methylpyridinium tetrafluoroborate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl- 3-Methylpyridinium bis (trifluoromethanesulfonyl) imide, 1-butyl-3-methylpyridinium bis (pentafluoroethanesulfonyl) imide, 1-hexylpyridinium tetrafluoroborate, 2-methyl-1-pyrrolinte tetrafluoroborate, 1 -Ethyl-2-phenylindole tetrafluoroborate, 1,2-dimethylindole tetrafluoroborate, 1-ethylcarbazole tetrafluoroborate, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazole Rium acetate, 1-ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3-methylimidazolium heptafluorobutyrate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methyl Imidazolium perfluorobutane sulfonate, 1-ethyl-3-methylimidazolium dicyanamide, 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-3-methylimidazolium bis (pentafluoroethanesulfonyl) ) Imid, 1-ethyl-3-methylimidazolium tris (trifluoromethanesulfonyl) imide,

1-Butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium trifluoroacetate, 1-butyl-3-methylimidazolium heptafluoro Butyrate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium perfluorobutanesulfonate, 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-hexyl -3-Methylimidazolium bromide, 1-hexyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium hexafluorophosphate, 1- Hexyl-3-methylimidazolium trifluoromethanesulfonate, 1-octyl-3-methylimidazolium tetrafluoroborate, 1-octyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-2,3-dimethylimidazolium Tetrafluoroborate, 1,2-dimethyl-3-propylimidazolium bis (trifluoromethanesulfonyl) imide, 1-methylpyrazolium tetrafluoroborate, 3-methylpyrazolium tetrafluoroborate, tetrahexylammonium bis (trifluoromethane) Sulfonyl) imide, diallyldimethylammonium tetrafluoroborate, diallyldimethylammonium trifluoromethanesulfonate, diallyldimethylammonium bis (trifluoromethanesulfonyl) imide, diallyldimethylammonium bis (pentafluoroethanesulfonyl) imide, N, N-diethyl-N-methyl -N- (2-methoxyethyl) ammonium tetrafluoroborate, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium trifluoromethanesulfonate, N, N-diethyl-N-methyl-N- ( 2-methoxyethyl) ammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (pentafluoroethanesulfonyl) imide, glycidyltrimethylammonium trifluoromethanesulfonate,

Glysidyltrimethylammonium bis (trifluoromethanesulfonyl) imide, glycidyltrimethylammonium bis (pentafluoroethanesulfonyl) imide, 1-butylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl-3-methylpyridinium (trifluoromethanesulfonyl) tri Fluoroacetamide, 1-ethyl-3-methylimidazolium (trifluoromethanesulfonyl) trifluoroacetamide, diallyldimethylammonium (trifluoromethanesulfonyl) trifluoroacetamide, glycidyltrimethylammonium (trifluoromethanesulfonyl) trifluoroacetamide, N, N-dimethyl -N-ethyl-N-propylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-butylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N -Pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-heptylammonium bis ( Trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-nonylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N, N-dipropylammonium bis (trifluoromethanesulfonyl) imide, N , N-dimethyl-N-propyl-N-butylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N -Propyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide,

N, N-dimethyl-N-propyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-butyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl- N-butyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-pentyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N, N-dihexylammonium Bis (trifluoromethanesulfonyl) imide, trimethylheptylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N-propylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl -N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-propyl-N-pentylammonium bis (Trifluoromethanesulfonyl) imide, triethylpropylammonium bis (trifluoromethanesulfonyl) imide, triethylpentylammonium bis (trifluoromethanesulfonyl) imide, triethylheptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-methyl- N-ethylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-butyl-N-hexylammonium bis (Trifluoromethanesulfonyl) imide, N, N-dipropyl-N, N-dihexylammonyl bis (trifluoromethanesulfonyl) imide, N, N-dibutyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N , N-dibutyl-N-methyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, trioctylmethylammonium bis (trifluoromethanesulfonyl) imide, N-methyl-N-ethyl-N-propyl-N-pentylammonium bis (Trifluoromethanesulfonyl) imide and the like can be mentioned.

Surfactants include glycerin fatty acid esters, sorbitan fatty acid esters, polyoxyethylene alkylamine fatty acid esters, polyoxyethylene alkylamines, N-hydroxyethyl-N-2-hydroxyalkylamines, and alkyldiethanolamides. Nonionic surfactants such as;
Anionic surfactants such as alkyl phosphate salts, alkyl sulfonates and alkylbenzene sulfonates;
Cationic surfactants such as quaternary ammonium salts and amide quaternary ammonium salts;
Amphoteric surfactants such as alkyl betaines and alkylimidazolinium betaines; and the like.

Examples of the conductive polymer include polythiophene, PEDOT-PSS (poly (3,4-ethylenedioxythiophene) -poly (styrene sulfonic acid)), polyaniline, polypyrrole, polyquinoxaline and the like. Among these, polythiophene and PEDOT-PSS are preferable.
In the present invention, the antistatic agent may be used alone or in combination of two or more.

The content of the antistatic agent contained in the base film (α) is not particularly limited, and can be appropriately determined according to the desired antistatic property.

The antistatic pressure-sensitive adhesive partial layer is a layer having adhesiveness and antistatic properties, and is a layer laminated directly or via another layer on the base film (α).
By providing the antistatic adhesive partial layer in the protective film, the gas barrier layer can be efficiently protected. Further, the surface resistivity of the surface (A) of the protective film can be easily set to 5.0 × 10 ¹¹ Ω / □ or less.

The thickness of the antistatic pressure-sensitive adhesive partial layer is not particularly limited. The thickness of the antistatic pressure-sensitive adhesive partial layer is usually 200 μm or less, preferably 5 to 100 μm, and more preferably 10 to 50 μm.

Examples of the antistatic pressure-sensitive adhesive partial layer include a layer containing a pressure-sensitive adhesive resin component and an antistatic agent.
The adhesive resin component is not particularly limited as long as it has appropriate adhesiveness and peelability.
Examples of such resin components include acrylic resins, urethane resins, silicone resins, rubber resins, polyester resins and the like.

Among these, acrylic resins are preferable because they have appropriate adhesiveness and peelability.
Examples of the acrylic resin include a repeating unit derived from an alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms and an acrylic copolymer having a repeating unit derived from a functional group-containing monomer.

Examples of the alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth). Examples thereof include acrylates, lauryl (meth) acrylates, tridecyl (meth) acrylates, and stearyl (meth) acrylates.

Examples of the functional group-containing monomer include a hydroxy group-containing monomer, a carboxy group-containing monomer, an epoxy group-containing monomer, an amino group-containing monomer, a cyano group-containing monomer, a keto group-containing monomer, and an alkoxysilyl group-containing monomer. Among these, as the functional group-containing monomer, a hydroxy group-containing monomer and a carboxy group-containing monomer are preferable.
Examples of the hydroxy group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth). Examples include acrylate.
Examples of the carboxy group-containing monomer include (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid and the like.

The antistatic pressure-sensitive adhesive partial layer may have a crosslinked structure formed therein. The crosslinked structure can be formed by a known method using a crosslinking agent.

The antistatic agent is not particularly limited as long as it can impart antistatic properties to the pressure-sensitive adhesive.
Examples of the antistatic agent include those similar to those shown as the antistatic agent in the base film (α).
The content of the antistatic agent contained in the antistatic pressure-sensitive adhesive partial layer is not particularly limited, and can be appropriately determined according to the desired antistatic property. The blending amount of the antistatic agent in the antistatic pressure-sensitive adhesive is preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive resin. When this compounding amount is 0.05 parts by mass or more, the antistatic performance is better exhibited. On the other hand, when the blending amount of the antistatic agent is 10 parts by mass or less, the balance between the antistatic performance and the durability of the adhesive is better. From such a viewpoint, the blending amount of the antistatic agent is preferably 0.05 to 5 parts by mass, more preferably 0.06 to 3 parts by mass.

The antistatic pressure-sensitive adhesive partial layer may contain other components such as a pressure-sensitive adhesive in addition to the pressure-sensitive adhesive resin component and the antistatic agent.

The laminated film (α) may have a layer other than the base film (α) and the antistatic pressure-sensitive adhesive partial layer. Examples of such a layer include an antistatic partial layer.
Examples of the antistatic partial layer include a layer containing an antistatic agent. Examples of the antistatic agent include those similar to those shown as the antistatic agent in the base film (α).
Examples of the laminated film (α) having an antistatic partial layer include a laminated film having a layer structure of an antistatic adhesive partial layer / a base film (α) / an antistatic partial layer.

The laminated film (α) can be produced, for example, by applying a pressure-sensitive adhesive coating liquid containing an antistatic agent or the like on a base film (α) and drying the obtained coating film.
The coating method and the drying method are not particularly limited, and known methods can be appropriately used.
Further, the laminated film (α) having the antistatic partial layer can be efficiently manufactured, for example, by forming the antistatic adhesive partial layer on the surface of a commercially available base film with an antistatic layer.

When the protective film is a laminated film (α), it is preferable that the antistatic pressure-sensitive adhesive partial layer is in contact with the gas barrier layer from the viewpoint of the surface resistivity of the surface (A) of the protective film.

[Gas barrier layer]
The gas barrier layer in the gas barrier property is a layer having a gas barrier property. The gas barrier property refers to the property of suppressing the permeation of a gas such as water vapor.
The thickness of the gas barrier layer is usually 1 to 300 μm, preferably 10 to 200 nm, and more preferably 20 to 200 nm.
The water vapor transmittance of the gas barrier layer in an atmosphere having a temperature of 40 ° C. and a relative humidity of 90% is preferably 0.100 g / m ² / day or less, more preferably 0.05 g / m ² / day or less, and further preferably 0. It is 3.03 g / m ² / day or less. There is no particular lower limit, and the smaller the value, the more preferable, but usually 0.001 g / m ² / day or more.
The transmittance of water vapor or the like in the gas barrier layer can be measured using a known gas permeability measuring device.

The layer structure of the gas barrier layer is not particularly limited. The gas barrier layer may have a single-layer structure or a multi-layer structure.
Since it is easy to form a gas barrier layer having the desired characteristics, the gas barrier layer preferably has a multilayer structure.

Examples of the gas barrier layer having a single-layer structure include those similar to the gas barrier partial layer in the laminated film (β) described later.
As the gas barrier layer having a multilayer structure, a laminated film having a base film (hereinafter, the base film constituting the gas barrier layer is referred to as “base film (β)”) and a gas barrier partial layer (hereinafter, this). A laminated film is referred to as a "laminated film (β)").

The thickness of the base film (β) is not particularly limited. The thickness of the base film (β) is usually 0.5 to 500 μm, preferably 1 to 100 μm.

As the base film (β), a resin film is usually used.
Resin components of the resin film include polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polysulfone, polyethersulfone, polyphenylene sulfide, acrylic resin, and cycloolefin polymer. , Aromatic polymers and the like.

Among these, polyester, polyamide or cycloolefin-based polymer is preferable, and polyester or cycloolefin-based polymer is more preferable because of its excellent transparency and versatility.

Examples of the polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate and the like, and polyethylene terephthalate is preferable.
Examples of the polyamide include all aromatic polyamides, nylon 6, nylon 66, nylon copolymers and the like.

Examples of the cycloolefin-based polymer include norbornene-based polymers, monocyclic cyclic olefin-based polymers, cyclic conjugated diene-based polymers, vinyl alicyclic hydrocarbon polymers, and hydrides thereof. Specific examples thereof include Apel (ethylene-cycloolefin copolymer manufactured by Mitsui Kagaku Co., Ltd.), Arton (norbornene-based polymer manufactured by JSR Corporation), Zeonoa (norbornene-based polymer manufactured by Zeon Corporation), and the like. ..

The resin film may contain various additives. Examples of the additive include an ultraviolet absorber, an antistatic agent, a stabilizer, an antioxidant, a plasticizer, a lubricant, a coloring pigment and the like. The content of these additives may be appropriately determined according to the purpose.

The resin film can be obtained by preparing a resin composition containing a resin component and, if desired, various additives, and molding the resin composition into a film. The molding method is not particularly limited, and known methods such as a casting method and a melt extrusion method can be used.

The gas barrier partial layer constituting the laminated film (β) is referred to as a gas barrier partial layer made of an inorganic vapor film, a gas barrier partial layer containing a gas barrier resin, and a layer containing a polymer compound (hereinafter referred to as “polymer layer”). In some cases, a gas barrier partial layer obtained by modifying the surface of) may be mentioned. In this case, the gas barrier partial layer does not mean only the modified region, but means "a polymer layer containing the modified region".
Among these, a gas barrier partial layer made of an inorganic thin-film film or a gas barrier partial layer having a modified surface of a polymer layer is preferable because a thin layer having excellent gas barrier properties can be efficiently formed.

Examples of the inorganic vapor deposition film include a vapor deposition film of an inorganic compound or a metal.
Inorganic oxides such as silicon oxide, aluminum oxide, magnesium oxide, zinc oxide, indium oxide, and tin oxide; inorganic nitrides such as silicon nitride, aluminum nitride, and titanium nitride; inorganic carbides; Examples thereof include inorganic sulfides; inorganic oxynitrides such as silicon oxide nitride; inorganic oxidative carbides; inorganic nitriding carbides; and inorganic oxynitride carbides.
Examples of the raw material of the metal vapor deposition film include aluminum, magnesium, zinc, tin and the like.
These can be used alone or in combination of two or more.

Among these, an inorganic vapor deposition film made from an inorganic oxide, an inorganic nitride or a metal is preferable from the viewpoint of gas barrier properties, and further, from the viewpoint of transparency, an inorganic vapor deposition made from an inorganic oxide or an inorganic nitride as a raw material is preferable. A membrane is preferred. Further, the inorganic vapor deposition film may be a single layer or a multilayer.

The thickness of the inorganic thin-film film is preferably in the range of 1 to 2000 nm, more preferably 3 to 1000 nm, more preferably 5 to 500 nm, and further preferably 40 to 200 nm from the viewpoint of gas barrier properties and handleability.

The method for forming the inorganic thin-film film is not particularly limited, and a known method can be used. Examples of the method for forming the inorganic vapor deposition film include a PVD method such as a vacuum vapor deposition method, a sputtering method, and an ion plating method, a CVD method such as a thermal CVD method, a plasma CVD method, and an optical CVD method, and an atomic layer deposition method ( ALD method).

Examples of the gas barrier resin include polyvinyl alcohol, a partially saponified product thereof, an ethylene-vinyl alcohol copolymer, polyacrylonitrile, polyvinyl chloride, polyvinylidene chloride, polychlorotrifluoroethylene, oxygen, water vapor, and the like. Examples include resins that are difficult to permeate.

The thickness of the gas barrier partial layer containing the gas barrier resin is preferably in the range of 1 to 2000 nm, more preferably 3 to 1000 nm, more preferably 5 to 500 nm, still more preferably 40 to 200 nm from the viewpoint of gas barrier properties.

Examples of the method for forming the gas barrier partial layer containing the gas barrier resin include a method in which a solution containing the gas barrier resin is applied on a protective film and the obtained coating film is appropriately dried.

The method for applying the resin solution is not particularly limited, and examples thereof include known application methods such as a spin coating method, a spray coating method, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, and a gravure coating method. ..
As a method for drying the coating film, conventionally known drying methods such as hot air drying, hot roll drying, and infrared irradiation can be used.

In the gas barrier partial layer in which the surface of the polymer layer is modified, the polymer compounds used include silicon-containing polymer compounds, polyimides, polyamides, polyamideimides, polyphenylene ethers, polyether ketones, polyether ether ketones, and polyolefins. , Polyester, polycarbonate, polysulfone, polyether sulfone, polyphenylene sulfide, polyarylate, acrylic resin, alicyclic hydrocarbon resin, aromatic polymer and the like.
These polymer compounds can be used alone or in combination of two or more.

In addition to the polymer compound, the polymer layer may contain other components as long as the object of the present invention is not impaired. Examples of other components include a curing agent, an antiaging agent, a light stabilizer, a flame retardant and the like.
The content of the polymer compound in the polymer layer is preferably 50% by mass or more, more preferably 70% by mass or more, because a gas barrier partial layer having more excellent gas barrier properties can be formed.

The thickness of the polymer layer is not particularly limited, but is usually 20 nm to 50 μm, preferably 30 nm to 1 μm, and more preferably 40 nm to 500 nm.

The polymer layer can be formed, for example, by applying a liquid in which a polymer compound is dissolved or dispersed in an organic solvent onto a protective film by a known coating method, and drying the obtained coating film.

Examples of the organic solvent include aromatic hydrocarbon solvents such as benzene and toluene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; n-pentane, n-hexane and n. -An aliphatic hydrocarbon solvent such as heptane; an alicyclic hydrocarbon solvent such as cyclopentane and cyclohexane; and the like can be mentioned.
These solvents can be used alone or in combination of two or more.

The coating method includes bar coating method, spin coating method, dipping method, roll coating method, gravure coating method, knife coating method, air knife coating method, roll knife coating method, die coating method, screen printing method, spray coating method, and gravure offset. The law etc. can be mentioned.

Examples of the method for drying the coating film include conventionally known drying methods such as hot air drying, hot roll drying, and infrared irradiation. The heating temperature is usually 80 to 150 ° C., and the heating time is usually several tens of seconds to several tens of minutes.

Examples of the method for modifying the surface of the polymer layer include ion implantation treatment, plasma treatment, ultraviolet irradiation treatment, heat treatment and the like.
The ion implantation treatment is a method of injecting accelerated ions into a polymer layer to modify the polymer layer, as will be described later.
Plasma treatment is a method of modifying a polymer layer by exposing the polymer layer to plasma. For example, plasma treatment can be performed according to the method described in Japanese Patent Application Laid-Open No. 2012-106421.
The ultraviolet irradiation treatment is a method of irradiating a polymer layer with ultraviolet rays to modify the polymer layer. For example, the ultraviolet modification treatment can be performed according to the method described in Japanese Patent Application Laid-Open No. 2013-226757.

Among these gas barrier properties, those obtained by subjecting a layer containing a silicon-based polymer compound to an ion implantation treatment are more preferable because they are more excellent in gas barrier properties.
Examples of the silicon-containing polymer compound include polysilazane-based compounds, polycarbosilane-based compounds, polysilane-based compounds, polyorganosiloxane-based compounds, poly (disylanilenphenylene) -based compounds, and poly (disylanilenene ethynylene) -based compounds. , And polysilazane compounds are more preferable.

A polysilazane compound is a compound having a repeating unit containing an —Si—N— bond (silazane bond) in the molecule. Specifically, equation (1)

A compound having a repeating unit represented by is preferable. The number average molecular weight of the polysilazane compound used is not particularly limited, but is preferably 100 to 50,000.

In the above equation (1), n represents an arbitrary natural number. Rx, Ry and Rz are independently hydrogen atom, alkyl group having unsubstituted or substituent, cycloalkyl group having unsubstituted or substituent, alkenyl group having unsubstituted or substituent, unsubstituted or substituted. Represents a non-hydrolytable group such as an aryl group having a group or an alkylsilyl group.

Examples of the alkyl group of the alkyl group having no substituent or substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a t-butyl group. Examples thereof include an alkyl group having 1 to 10 carbon atoms such as an n-pentyl group, an isopentyl group, a neopentyl group, an n-hexyl group, an n-heptyl group and an n-octyl group.

Examples of the cycloalkyl group of the cycloalkyl group having no substituent or substituent include a cycloalkyl group having 3 to 10 carbon atoms such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a cycloheptyl group.

Examples of the alkenyl group of the alkenyl group having no substituent or substituent include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group and the like having 2 to 2 carbon atoms. Included are 10 alkenyl groups.

Examples of the substituent of the alkyl group, cycloalkyl group and alkenyl group include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxyl group; thiol group; epoxy group; glycidoxy group; (meth) acryloyloxy group. An aryl group having an unsubstituted or substituent such as a phenyl group, a 4-methylphenyl group, a 4-chlorophenyl group; and the like can be mentioned.

Examples of the aryl group of the aryl group having an unsubstituted or substituent include an aryl group having 6 to 15 carbon atoms such as a phenyl group, a 1-naphthyl group and a 2-naphthyl group.

The substituent of the aryl group includes a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group; and a carbon number such as a methoxy group and an ethoxy group. 1 to 6 alkoxy groups; nitro group; cyano group; hydroxyl group; thiol group; epoxy group; glycidoxy group; (meth) acryloyloxy group; phenyl group, 4-methylphenyl group, 4-chlorophenyl group, etc. An aryl group having a substituent; and the like can be mentioned.

Examples of the alkylsilyl group include a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, a trit-butylsilyl group, a methyldiethylsilyl group, a dimethylsilyl group, a diethylsilyl group, a methylsilyl group, an ethylsilyl group and the like.

Among these, as Rx, Ry, and Rz, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group is preferable, and a hydrogen atom is particularly preferable.

The polysilazane compound having a repeating unit represented by the formula (1) is any of inorganic polysilazane in which Rx, Ry and Rz are all hydrogen atoms, and organic polysilazane in which at least one of Rx, Ry and Rz is not a hydrogen atom. May be.

Further, in the present invention, a modified polysilazane can also be used as the polysilazane compound. Examples of the polysilazane modified product include JP-A-62-195024, JP-A-2-844437, JP-A-63-81122, JP-A-1-138108, and JP-A No. 2-175726. , Japanese Patent Application Laid-Open No. 5-238827, Japanese Patent Application Laid-Open No. 5-238827, Japanese Patent Application Laid-Open No. 6-122852, Japanese Patent Application Laid-Open No. 6-306329, Japanese Patent Application Laid-Open No. 6-299118, Japanese Patent Application Laid-Open No. 9-313333, Examples thereof include those described in Kaihei 5-345926 and Japanese Patent Application Laid-Open No. 4-63833.
Among these, as the polysilazane compound, perhydropolysilazane in which Rx, Ry, and Rz are all hydrogen atoms is preferable from the viewpoint of easy availability and the ability to form an ion-implanted layer having excellent gas barrier properties.
Further, as the polysilazane compound, a commercially available product commercially available as a glass coating material or the like can be used as it is.
The polysilazane-based compound can be used alone or in combination of two or more.

The ions to be injected into the polymer layer include rare gas ions such as argon, helium, neon, krypton, and xenone; ions such as fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, and sulfur; methane, ethane, etc. Alken gas ions; Alken gas ions such as ethylene and propylene; Alkene gas ions such as pentadiene and butadiene; Alkin gas ions such as acetylene; Aromatic carbonization such as benzene and toluene Hydrogen-based gas ions; cycloalkane-based gas ions such as cyclopropane; cycloalkene-based gas ions such as cyclopentene; metal ions; organic silicon compound ions; and the like.
These ions can be used alone or in combination of two or more.
Among these, rare gas ions such as argon, helium, neon, krypton, and xenon are preferable because ions can be injected more easily and a gas barrier partial layer having better gas barrier properties can be formed. ..

The amount of ions injected can be appropriately determined according to the purpose of use of the gas barrier adhesive film (necessary gas barrier property, transparency, etc.) and the like.

Examples of the method of injecting ions include a method of irradiating ions (ion beams) accelerated by an electric field, a method of injecting ions in plasma, and the like. Among them, the latter method of implanting ions in plasma (plasma ion implantation method) is preferable because the target gas barrier partial layer can be easily formed.

In the plasma ion injection method, for example, plasma is generated in an atmosphere containing a plasma-generating gas such as a rare gas, and a negative high-voltage pulse is applied to the polymer layer to generate ions (cations) in the plasma. , Can be performed by injecting into the surface portion of the polymer layer. More specifically, the plasma ion implantation method can be carried out by the method described in the WO2010 / 107018 pamphlet or the like.

By ion implantation, the thickness of the region where ions are implanted can be controlled by the implantation conditions such as the type of ions, the applied voltage, and the processing time, and is determined according to the thickness of the polymer layer and the purpose of use of the laminate. However, it is usually 10 to 400 nm in the depth direction from the surface of the polymer layer.

The injection of ions can be confirmed by performing elemental analysis measurement near 10 nm from the surface of the polymer layer using X-ray photoelectron spectroscopy (XPS).

The laminated film (β) may have other layers. Examples of other layers include a primer layer, a conductive layer, a hard coat layer and the like.

[Adhesive resin layer]
The adhesive resin layer in the adhesive unit is a layer used for adhesion to an object.
In the present invention, the adhesive resin means a bonding agent such as a pressure-sensitive adhesive, an adhesive, and a pressure-sensitive adhesive.

The thickness of the adhesive resin layer can be appropriately selected in consideration of the purpose of use of the gas barrier adhesive film and the like. The thickness is usually 0.1 to 1000 μm, preferably 0.5 to 500 μm, more preferably 1 to 100 μm, still more preferably 1 to 30 μm.
If it is 0.1 μm or more, a gas barrier adhesive film having sufficient adhesive strength or adhesive strength can be obtained. When it is 1000 μm or less, the bendability of the gas barrier adhesive film is good, and it is advantageous in terms of productivity and handleability.

The water vapor transmittance of the adhesive resin layer is preferably 100 g / m ² / day or less, and more preferably 50 g / m ² / day or less in terms of thickness of 50 μm.
When the water vapor permeability (50 μm thickness conversion value) of the adhesive resin layer is 100 g / m ² / day or less, the infiltration of water vapor or the like from the end portion of the adhesive resin layer can be further suppressed. A gas barrier adhesive film having such an adhesive resin layer is preferably used as a material for forming a sealing material.
The water vapor permeability of the adhesive resin layer can be measured, for example, by forming an adhesive resin layer on a support having a low gas barrier property such as a polyethylene terephthalate film as a sample. Further, the water vapor transmittance can be calculated when the thickness is 50 μm by utilizing the fact that the water vapor transmittance is inversely proportional to the thickness of the adhesive resin layer.

Examples of the adhesive resin layer include those formed by using an adhesive resin such as a rubber-based adhesive resin, a polyolefin-based adhesive resin, an epoxy-based adhesive resin, and a silicone-based adhesive resin.
By using these adhesive resins, it is possible to efficiently form an adhesive resin layer having excellent gas barrier properties.
In particular, since it is easy to obtain an adhesive resin layer having better gas barrier properties, it is preferable to form an adhesive resin layer using a polyolefin-based adhesive resin.

As the rubber-based adhesive resin, a modified natural rubber obtained by graft-polymerizing one or more monomers selected from (meth) acrylic acid alkyl ester, styrene and (meth) acrylonitrile with natural rubber or natural rubber. Adhesive resin mainly composed of isoprene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, methyl methacrylate-butadiene rubber, urethane rubber, polyisoprene resin, polybutene resin, etc. Can be mentioned.

Among the rubber-based adhesive resins, an adhesive resin containing polyisobutylene-based resin as a main component is preferable. Examples of the polyisobutylene resin include homobutylene homopolymers, isobutylene and isoprene copolymers, isobutylene and n-butene copolymers, isobutylene and butadiene copolymers, and homopolymers or copolymers thereof. Examples thereof include halogenated butyl rubber obtained by brominating or chlorinating the coalescence. These resins may be used alone or in combination of two or more. When the polyisobutylene-based resin is a copolymer, it is assumed that the structural unit composed of isobutylene is contained in the largest amount among all the monomer components.
The mass average molecular weight of the polyisobutylene resin is preferably 10,000 to 600,000, more preferably 100,000 to 500,000.
As used herein, the term "main component" refers to a component that accounts for 50% by mass or more of the solid content (the same applies hereinafter).

Examples of the polyolefin-based adhesive resin include an adhesive resin containing a modified polyolefin resin as a main component.
The modified polyolefin resin is a polyolefin resin into which a functional group is introduced, which is obtained by subjecting a polyolefin resin as a precursor to a modification treatment using a modifier.

The polyolefin resin includes ultra-low density polyethylene (VLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene, polypropylene (PP), and ethylene-propylene. Examples thereof include a polymer, an olefin-based elastomer (TPO), an ethylene-vinyl acetate copolymer (EVA), an ethylene- (meth) acrylic acid copolymer, and a polyethylene- (meth) acrylic acid ester copolymer.

The denaturing agent used for the modification treatment of the polyolefin resin is a compound having a functional group in the molecule that can contribute to the cross-linking reaction.
Functional groups include carboxyl group, carboxylic acid anhydride group, carboxylic acid ester group, hydroxyl group, epoxy group, amide group, ammonium group, nitrile group, amino group, imide group, isocyanate group, acetyl group, thiol group and ether group. , Thioether group, sulfone group, phosphon group, nitro group, urethane group, halogen atom and the like. Among these, a carboxyl group, a carboxylic acid anhydride group, a carboxylic acid ester group, a hydroxyl group, an ammonium group, an amino group, an imide group and an isocyanate group are preferable, a carboxylic acid anhydride group and an alkoxysilyl group are more preferable, and a carboxylic acid anhydride is used. The physical group is particularly preferable.

Examples of the epoxy-based adhesive resin include hydrocarbon-modified epoxy resins such as fatty chain-modified epoxy resin, cyclopentadiene-modified epoxy resin, and naphthalene-modified epoxy resin, elastomer-modified epoxy resin, and silicone-modified epoxy resin as main components. Can be mentioned.

Examples of the silicone-based adhesive resin include an adhesive resin having a polyorganosiloxane or the like having a functional group capable of contributing to a cross-linking reaction in the side chain.

These adhesive resins can be used as a curing agent, a cross-linking agent, a polymerization initiator, a light stabilizer, an antioxidant, a tackifier, a plasticizer, an ultraviolet absorber, a colorant, a resin stabilizer, and a filler. , Pigments, bulking agents, antistatic agents and the like may be contained.
These components can be appropriately selected and used according to each adhesive resin.

For the adhesive resin layer, for example, a coating liquid for forming an adhesive resin layer is prepared, this is applied on a release film, the obtained coating film is dried, and if necessary, it is heated or irradiated with active energy rays. It can be formed by curing it.
The coating method, the drying method, and the curing method are not particularly limited, and known methods can be appropriately used.

[Release film]
The release film in the adhesive unit is a film for protecting the adhesive resin layer during transportation and storage of the gas barrier adhesive film, and is finally removed by peeling.

The surface of the release film on the adhesive resin layer side (the surface in contact with the adhesive resin layer in the gas barrier adhesive film; hereinafter, may be referred to as "surface (C)") and the other surface (gas barrier adhesive). In the film, the surface that is exposed to the outside. Hereinafter, it may be referred to as “surface (D)”), the surface resistance of at least one of them is 5.0 × 10 ¹¹ Ω / □ or less. The surface resistivity of the surface (C) is usually 1.0 × 10 ¹⁰ Ω / □ or more and 5.0 × 10 ¹¹ Ω / □ or less, and the surface resistivity of the surface (D) is usually 1.0. × 10 ⁷ Ω / □ or more and 5.0 × 10 ¹¹ Ω / □ or less.

By setting the surface resistivity of at least one of the surface (C) and the surface (D) to 5.0 × 10 ¹¹ Ω / □ or less, the charge amount of the adhesive resin layer is reduced after the release film is peeled off. It can be made smaller.

In particular, the gas barrier adhesive film having a small surface resistivity of the surface (D) can easily peel off the gas barrier adhesive films when a plurality of gas barrier adhesive films are stacked or wound in a roll shape. Because it is a thing, it is superior in workability.

The thickness of the release film is not particularly limited, but is usually 1 to 300 μm, preferably 10 to 100 μm.
The layer structure of the release film is not particularly limited. The release film may have a single-layer structure or may have a multi-layer structure.
Since it is easy to obtain a release film having the desired characteristics, the release film preferably has a multilayer structure.

The release film having a multilayer structure includes a base film (hereinafter, the base film constituting the release film is referred to as "base film (γ)"), an antistatic partial layer, and a peelable partial layer. However, a laminated film in which one outermost layer is a peelable partial layer (hereinafter, this laminated film is referred to as a “laminated film (γ)”) can be mentioned.
The layer structure of the laminated film (γ) includes “base film (γ) / antistatic partial layer / peelable partial layer” and “antistatic partial layer / base film (γ) / peelable partial layer”. ".

Examples of the base film (γ) include those similar to those shown as the base film (α).
The base film (γ) preferably contains an antistatic agent. By using the base film (γ) containing an antistatic agent, the surface resistivity of the surfaces (C) and (D) of the release film can be lowered more efficiently. Examples of the antistatic agent include those similar to those shown as the antistatic agent in the base film (α).
The content of the antistatic agent in the base film (γ) is not particularly limited and can be appropriately determined according to the desired antistatic property.

The antistatic partial layer is a layer having antistatic properties (meaning the property of being able to release static electricity (voltage band) quickly. The lower the surface resistivity, the better the antistatic properties), and the base film (γ). A layer laminated on top, either directly or via other layers.
By providing the antistatic partial layer in the release film, the surface resistivity of the surface (C) of the release film can be easily reduced to 5.0 × 10 ¹¹ Ω / □ or less.

The thickness of the antistatic partial layer is not particularly limited. The thickness of the antistatic partial layer is usually 10 μm or less, preferably 0.01 to 5 μm, and more preferably 0.03 to 3 μm.
Examples of the antistatic partial layer include a layer containing a resin component and an antistatic agent.
The resin component is not particularly limited as long as it can fix the antistatic agent.
Examples of such resin components include acrylic resins, urethane resins, silicone resins, rubber resins, polyester resins and the like.

The antistatic agent may be any antistatic agent and is not particularly limited.
Examples of the antistatic agent include those similar to those shown as the antistatic agent in the base film (α).
The content of the antistatic agent contained in the antistatic partial layer is not particularly limited, and can be appropriately determined according to the desired antistatic property.

The peelable partial layer is a layer having peelability and constitutes one outermost layer of the release film. In the gas barrier adhesive film of the present invention, by adjoining the peelable partial layer to the adhesive resin layer, the adhesive resin layer of the gas barrier adhesive film of the present invention can be exposed more efficiently.

The thickness of the peelable partial layer is not particularly limited, but is usually 0.01 to 3.0 μm, preferably 0.03 to 2.0 μm.

The peelable partial layer can be formed by using a peeling agent.
Examples of the release agent include olefin resins such as polyethylene and polypropylene; rubber elastomers such as isoprene resins and butadiene resins; long-chain alkyl resins; alkyd resins; fluororesins; silicone resins; and the like. Can be mentioned.

The laminated film (γ) is formed, for example, by applying a coating liquid containing an antistatic agent or the like on a base film (γ) and drying the obtained coating film to form an antistatic partial layer. It can be produced by applying a release agent on the antistatic partial layer and drying the obtained coating film to form a releaseable partial layer.
The coating method and the drying method are not particularly limited, and known methods can be appropriately used.

[Gas barrier adhesive film]
The gas barrier adhesive film of the present invention has the gas barrier unit and the adhesive unit, and the adhesive resin layer of the adhesive unit is directly on the gas barrier layer of the gas barrier unit or another layer. The protective film and the release film each form an outermost layer.

Examples of the gas barrier adhesive film of the present invention include those shown in FIGS. 1 and 2.
The gas barrier adhesive film (1) shown in FIG. 1 (A) has a gas barrier unit (4) composed of a protective film (2) / a gas barrier layer (3) and an adhesive resin layer (5) / release film (6). It has an adhesive unit (7) made of, and the adhesive resin layer (5) is directly laminated on the gas barrier layer (3), and the protective film (2) and the release film (6) are formed. Each has a layer structure constituting the outermost layer.

Further, as shown in FIG. 1 (B), the protective film (2) has a surface (A) (8) and a surface (B) (9). The surface resistivity of the surfaces (A) and (8) is 5.0 × 10 ¹¹ Ω / □ or less.
On the other hand, the release film (6) has a surface (C) (10) and a surface (D) (11). The surface resistivity of at least one of the surfaces of the surface (C) (10) and the surface (D) (11) is 5.0 × 10 ¹¹ Ω / □ or less.

The gas barrier adhesive film (12) shown in FIG. 2 is an adhesive composed of a gas barrier unit (15) composed of a protective film (13) / a gas barrier layer (14) and an adhesive resin layer (16) / a release film (17). It has a sex unit (18), and the adhesive resin layer (16) is laminated on the gas barrier layer (14) via another layer (19), and is laminated with the protective film (13). Each of the release films (17) constitutes the outermost layer.
Also in the gas barrier adhesive film (12) shown in FIG. 2, the surface resistivity of the surface (A) of the protective film (13) (the surface opposite to the gas barrier layer (14) side) is 5.0 × 10 ¹¹ . Ω / □ or less, the surface (C) (the surface adjacent to the adhesive resin layer (16)) and the surface (D) (the surface opposite to the adhesive resin layer (16) side) of the release film (17). ), The surface resistivity of at least one of the surfaces is 5.0 × 10 ¹¹ Ω / □ or less.

When the gas barrier adhesive film of the present invention has another layer like the gas barrier adhesive film (12), examples of the other layers include a primer layer, a conductor layer, a refractive index adjusting layer, and a dye layer. Be done.

The substantial thickness of the gas barrier adhesive film of the present invention (total thickness of the layers other than the protective film and the release film) is usually 1 to 300 μm, preferably 5 to 200 μm, and more preferably 10 to 150 μm.

The method for producing the gas barrier adhesive film of the present invention is not particularly limited.
For example, the gas barrier adhesive film of the present invention has a gas barrier property after obtaining a laminate for a gas barrier unit composed of a protective film and a gas barrier layer and a laminate for an adhesive unit composed of an adhesive resin layer and a release film, respectively. Manufactured by stacking the gas barrier layer of the unit laminate and the adhesive resin layer of the adhesive unit laminate so as to face each other, and adhering the gas barrier unit laminate and the adhesive unit laminate. be able to.

The gas barrier adhesive film of the present invention is hard to be charged after the protective film and the release film are peeled off and removed. Therefore, even when the organic EL element is attached to the organic EL element or the like, it is unlikely to cause a failure of the organic EL element or the like.
Further, the gas barrier adhesive film of the present invention is less likely to cause problems such as curling, adhesion of dust, and adhesion between films due to charging, and is excellent in workability in the pasting work.

Due to these characteristics, the gas barrier adhesive film of the present invention is suitably used as an adhesive film for electronic members or optical members. In particular, by using the gas barrier adhesive film of the present invention, it is possible to efficiently form a sealing material such as an organic EL element.

The method of using the gas barrier adhesive film of the present invention is not particularly limited. For example, the release film can be peeled off to expose the adhesive resin layer, the adhesive resin layer can be pressure-bonded to an organic EL element or the like, and then the protective film can be peeled off to seal the organic EL element. can.

Similarly, the moisture resistance of the electronic member or the optical member can be improved by crimping the exposed adhesive resin layer with another electronic member or the optical member and then peeling off the protective film.

2) Electronic member or optical member provided with a gas barrier adhesive film The electronic member and optical member of the present invention are characterized by comprising a gas barrier layer and an adhesive resin layer derived from the above gas barrier adhesive film.
The gas barrier adhesive film of the present invention can be preferably applied to devices whose performance deteriorates due to chemical components in the air (oxygen, water, nitrogen oxides, sulfur oxides, ozone, etc.).
In the electronic member and the optical member of the present invention, for example, the release film of the gas barrier adhesive film is peeled off to expose the adhesive resin layer, which is then attached to a predetermined surface of the device body, and then the adhesive resin layer is exposed. It can be obtained by peeling off the protective film.

Examples of the electronic member include a liquid crystal display member, an organic EL display member, an inorganic EL display member, an electronic paper member, a solar cell, a flexible substrate such as a thermoelectric conversion member, and the like.
Examples of the optical member include an optical filter, a wavelength conversion device, a dimming device, a polarizing plate, an optical member of a retardation plate, and the like.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
Parts and% in each example are based on mass unless otherwise specified.

[Manufacturing Example 1] Preparation of Gas Barrier Film A coating agent containing perhydropolysilazane as a main component (Aquamica NL110 manufactured by AZ Electronic Materials Co., Ltd.) is applied to one side of a polyethylene terephthalate film (PET23U403 manufactured by Toray Industries, Inc.). The obtained coating film was dried at 120 ° C. for 2 minutes to form a polysilazane layer having a thickness of 150 nm.
The obtained polysilazane layer was implanted with a plasma ion implanter (RF power supply: JEOL Ltd., RF56000, high voltage pulse power supply: Kurita Seisakusho Co., Ltd., PV-3-HSHV-0835) under the following conditions. Plasma ion implantation was performed to form a gas barrier layer (gas barrier partial layer).

Plasma generated gas: Ar
Gas flow rate: 100 sccm
Duty ratio: 0.5%
Applied voltage: -6kV
RF power supply: Frequency 13.56MHz, applied power 1000W
Chamber internal pressure: 0.2Pa
Pulse width: 5 μsec
Processing time (ion implantation time): 200 seconds

[Production Example 2] Preparation of coating liquid for forming an antistatic layer A solution obtained by diluting a mixture (PEDOT-PSS) of a water-soluble hydroxyl group-containing polyester resin, polyethylene dioxythiophene and polystyrene sulfonate with dimethyl sulfoxide and water (Chukyo Yushi Co., Ltd.) 1. A solution of water-soluble methylol melamine diluted with water per 100 parts of T-795 (solid content 5.1%) manufactured by Chukyo Yushi Co., Ltd. (P-695: solid content 70.0%). 0 part and 1.0 part of leveling agent (R-438: solid content 10.0%) manufactured by Chukyo Yushi Co., Ltd. are mixed, and then a mixed solvent of water and IPA (isopropyl alcohol) (mass ratio 1: 1) is further mixed. ) Was added to prepare a coating solution (solid content: 0.6%) for forming an antistatic layer.

[Production Example 3] Preparation of coating liquid for forming a release layer Organosiloxane oligomer (manufactured by Shin-Etsu Chemical Co., Ltd., X-62) with respect to 100 parts of polyorganosilane (manufactured by Shin-Etsu Chemical Co., Ltd., KS-847H: solid content 30%). -1378: Solid content 100%) 1.6 parts were mixed, and a mixed solution of toluene and MEK (methylethylketone) (mass ratio 1: 2.3) was further added. Next, 2.0 parts of a platinum catalyst (manufactured by Shin-Etsu Chemical Co., Ltd., solid content 2.0%), 10.0 parts of acetyl alcohol (manufactured by Shin-Etsu Chemical Co., Ltd., 100% solid content), and toluene having the above mass ratio were added to this product. And MEK were added to prepare a coating liquid (solid content: 1.4%) for forming a release layer.

[Production Example 4] Preparation of Antistatic Acrylic Adhesive -2-ethylhexyl acrylate / butyl acrylate / ethoxylated acrylic acid / -4-hydroxybutyl acrylate = 67/20/10/3 (mass ratio) The polymerization was carried out to obtain an acrylic acid ester copolymer. To 100 parts of a solution (solid content 48%) obtained by dissolving this acrylic acid ester copolymer in ethyl acetate, 1.1 parts of potassium hexafluorophosphate (solid content 100%) and a tin compound (toyochem) Co., Ltd., BXX3778: solid content 2.5%) 0.2 part, isocyanate cross-linking agent (Toyochem Co., Ltd., BXX6269: solid content 75%) 1.8 parts, acetylacetone (Toyochem Co., Ltd., BXX5638: solid content) 100%) 0.96 parts and toluene were added to prepare an antistatic acrylic pressure-sensitive adhesive (solid content 40.1%).

[Production Example 5] Preparation of Acrylic Adhesive for Protective Film Copolymerize butyl acrylate / -2-ethylhexyl acrylate / -2-hydroxyethyl acrylate = 76/19/5 (mass ratio) and combine with acrylic acid ester. A polymer was obtained. An isocyanate cross-linking agent (K-200: 100% solid content) 1 part of a solution (40% solid content) obtained by dissolving this acrylic acid ester copolymer in ethyl acetate. .6 parts, aluminum chelate cross-linking agent (manufactured by Saiden Chemical Co., Ltd., M-5: solid content 5.0%) 2.0 parts, and MEK were added to prepare an acrylic pressure-sensitive adhesive (solid content 32.4%). did.

[Production Example 6] Preparation of olefin-based pressure-sensitive adhesive A tackifier (Nippon Zeon Co., Ltd.) is applied to 100 parts of a toluene solution (solid content: 15%) of an isobutylene-isoprene copolymer (Butyl 365, manufactured by Nippon Butyl Co., Ltd.). Olefin-based adhesive An agent (solid content 15%) was prepared.

[Production Example 7] Production of release film (1) The antistatic layer forming coating solution obtained in Production Example 2 was applied to one side of a polyethylene terephthalate film (PET38T-100 manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.). The obtained coating film was dried to form an antistatic layer. Next, the coating liquid for forming a release layer obtained in Production Example 3 was applied to the side opposite to the antistatic layer of the polyethylene terephthalate film, and the obtained coating film was dried to form a silicone release layer. , A release film (1) was obtained.

[Production Example 8] Production of release film (2) The antistatic layer forming coating solution obtained in Production Example 2 was applied to one side of a polyethylene terephthalate film (PET38T-100 manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.). The obtained coating film was dried to form an antistatic layer. Next, the coating liquid for forming a release layer obtained in Production Example 3 was applied onto the antistatic layer, and the obtained coating film was dried to form a silicone release layer to obtain a release film (2). ..

[Production Example 9] Production of release film (3) The antistatic layer forming coating solution obtained in Production Example 2 was applied to one side of a polyethylene terephthalate film (PET38T-100 manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.). The obtained coating film was dried to form an antistatic layer. Next, the coating liquid for forming the antistatic layer was applied again on the side opposite to the antistatic layer of the polyethylene terephthalate film, and the obtained coating film was dried to form the antistatic layer.
Next, the release layer forming coating solution obtained in Production Example 3 was applied onto one of the antistatic layers, and the obtained coating film was dried to form a silicone release layer to obtain a release film (3). rice field.

[Production Example 10] Production of release film (4) A coating liquid for forming a release layer obtained in Production Example 3 is applied to one side of a polyethylene terephthalate film (PET38T-100 manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.). A release film (4) was obtained by drying the obtained coating film to form a silicone release layer.

The layered structures of the release films (1) to (4) obtained in Production Examples 7 to 10 are shown in FIG.
3 (A), (B), (C), and (D) show the layer structures of the release film (1), the release film (2), the release film (3), and the release film (4), respectively.

[Manufacturing Example 11] Production of Protective Film (1) with Release Film After drying the antistatic acrylic pressure-sensitive adhesive obtained in Production Example 4 on the release-treated surface of the release film (SP-PET381311 manufactured by Lintec Corporation). It was applied so as to have a thickness of 15 μm, and the obtained coating film was dried to form an antistatic pressure-sensitive adhesive layer. Next, a polyethylene terephthalate film (PET50A4300, manufactured by Toyobo Co., Ltd.) was superposed on the pressure-sensitive adhesive layer and pressure-bonded to obtain a protective film (1) with a release film.

[Manufacturing Example 12] Production of Protective Film (2) with Release Film After drying the antistatic acrylic pressure-sensitive adhesive obtained in Production Example 4 on the release-treated surface of the release film (SP-PET381311 manufactured by Lintec Corporation). It was applied so as to have a thickness of 15 μm, and the obtained coating film was dried to form an antistatic pressure-sensitive adhesive layer. Next, the pressure-sensitive adhesive layer is laminated on the surface opposite to the antistatic layer of the polyethylene terephthalate film with antistatic layer (PET38T-100G, manufactured by Mitsubishi Chemical Polyester Co., Ltd.) and pressure-bonded to form a protective film with a release film. (2) was obtained.

[Production Example 13] Production of Protective Film (3) with Release Film The acrylic pressure-sensitive adhesive obtained in Production Example 5 has a thickness of 15 μm on the release-treated surface of the release film (SP-PET38131C manufactured by Lintec Corporation). The coating film was dried so as to form an adhesive layer. Next, a polyethylene terephthalate film (PET50A4300, manufactured by Toyobo Co., Ltd.) was superposed on the pressure-sensitive adhesive layer and pressure-bonded to obtain a protective film (3) with a release film.

[Production Example 14] Production of Protective Film (4) with Release Film The acrylic pressure-sensitive adhesive obtained in Production Example 5 has a thickness of 25 μm after drying on the release-treated surface of the release film (SP-PET381311 manufactured by Lintec Corporation). The coating film was dried so as to form an adhesive layer. Next, the pressure-sensitive adhesive layer is laminated on the surface opposite to the antistatic layer of the polyethylene terephthalate film with antistatic layer (PET38T-100G, manufactured by Mitsubishi Chemical Polyester Co., Ltd.) and pressure-bonded to form a protective film with a release film. (4) was obtained.

FIG. 4 shows the layered structures of the protective films (1) to (4) with a release film obtained in Production Examples 11 to 14.
4 (A), (B), (C), and (D) show a protective film with a release film (1), a protective film with a release film (2), a protective film with a release film (3), and a release film, respectively. The layer structure of the protective film (4) is shown.

[Example 1]
While peeling off the release film of the protective film with release film (1) obtained in Production Example 11, the exposed adhesive layer is on the opposite side of the gas barrier layer (gas barrier partial layer) of the gas barrier film obtained in Production Example 1. By stacking and crimping on the surface, a laminated body for a gas barrier unit was obtained.
Separately from this, the olefin-based pressure-sensitive adhesive obtained in Production Example 6 was applied to the peeling surface of the release film (1) obtained in Production Example 7 so that the thickness after drying was 12 μm, and the obtained coating film was obtained. Was dried to form an adhesive resin layer to obtain a laminate for an adhesive unit.
Next, this adhesive resin layer was overlapped with the gas barrier film surface of the laminated body for the gas barrier unit and pressure-bonded to obtain a gas barrier adhesive film (1).
The layer structure of the gas barrier adhesive film (1) is shown in FIG. 5 (A).

[Example 2]
A gas barrier adhesive film (2) was obtained in the same manner as in Example 1 except that the protective film with a release film (2) was used instead of the protective film with a release film (1).
The layer structure of the gas barrier adhesive film (2) is shown in FIG. 5 (B).

[Example 3]
While peeling off the release film of the protective film with release film (1) obtained in Production Example 11, the exposed adhesive layer is on the opposite side of the gas barrier layer (gas barrier partial layer) of the gas barrier film obtained in Production Example 1. By stacking and crimping on the surface, a laminated body for a gas barrier unit was obtained.
Separately from this, the olefin-based pressure-sensitive adhesive obtained in Production Example 6 was applied to the peeling surface of the release film (2) obtained in Production Example 8 so that the thickness after drying was 12 μm, and the obtained coating film was obtained. Was dried to form an adhesive resin layer to obtain a laminate for an adhesive unit.
Next, this adhesive resin layer was overlapped with the gas barrier film surface of the laminated body for the gas barrier unit and pressure-bonded to obtain a gas barrier adhesive film (3).
The layer structure of the gas barrier adhesive film (3) is shown in FIG. 6 (A).

[Example 4]
A gas barrier adhesive film (4) was obtained in the same manner as in Example 3 except that the protective film with a release film (2) was used instead of the protective film with a release film (1).
The layer structure of the gas barrier adhesive film (4) is shown in FIG. 6 (B).

[Example 5]
While peeling off the release film of the protective film with release film (1) obtained in Production Example 11, the exposed adhesive layer is on the opposite side of the gas barrier layer (gas barrier partial layer) of the gas barrier film obtained in Production Example 1. By stacking and crimping on the surface, a laminated body for a gas barrier unit was obtained.
Separately from this, the olefin-based pressure-sensitive adhesive obtained in Production Example 6 was applied to the peeling surface of the release film (3) obtained in Production Example 9 so that the thickness after drying was 12 μm, and the obtained coating film was obtained. Was dried to form an adhesive resin layer to obtain a laminate for an adhesive unit.
Next, this adhesive resin layer was overlapped with the gas barrier film surface of the laminated body for the gas barrier unit and pressure-bonded to obtain a gas barrier adhesive film (5).
The layer structure of the gas barrier adhesive film (5) is shown in FIG. 7 (A).

[Example 6]
A gas barrier adhesive film (6) was obtained in the same manner as in Example 5 except that the protective film with a release film (2) was used instead of the protective film with a release film (1).
The layer structure of the gas barrier adhesive film (6) is shown in FIG. 7 (B).

[Comparative Example 1]
While peeling off the release film of the protective film with release film (3) obtained in Production Example 13, the exposed adhesive layer is on the opposite side of the gas barrier layer (gas barrier partial layer) of the gas barrier film obtained in Production Example 1. By stacking and crimping on the surface, a laminated body for a gas barrier unit was obtained.
Separately from this, the olefin-based pressure-sensitive adhesive obtained in Production Example 6 was applied to the peeling surface of the release film (4) obtained in Production Example 10 so that the thickness after drying was 12 μm, and the obtained coating film was obtained. Was dried to form an adhesive resin layer to obtain a laminate for an adhesive unit.
Next, this adhesive resin layer was overlapped with the gas barrier film surface of the laminated body for the gas barrier unit and pressure-bonded to obtain a gas barrier adhesive film (7).
The layer structure of the gas barrier adhesive film (7) is shown in FIG. 8 (A).

[Comparative Example 2]
A gas barrier adhesive film (8) was obtained in the same manner as in Example 1 except that the protective film with a release film (4) was used instead of the protective film with a release film (1).
The layer structure of the gas barrier adhesive film (8) is shown in FIG. 8 (B).

[Comparative Example 3]
A gas barrier adhesive film (9) was obtained in the same manner as in Example 3 except that the protective film with a release film (4) was used instead of the protective film with a release film (1).
The layer structure of the gas barrier adhesive film (9) is shown in FIG. 9 (A).

[Comparative Example 4]
A gas barrier adhesive film (10) was obtained in the same manner as in Example 5 except that the protective film with a release film (4) was used instead of the protective film with a release film (1).
The layer structure of the gas barrier adhesive film (10) is shown in FIG. 9 (B).

The gas barrier adhesive films (1) to (10) obtained in Examples and Comparative Examples were evaluated as follows. The results are shown in Table 1.
[Surface resistivity]
The protective film of the gas barrier adhesive film was peeled off, and the surface resistivity was measured on both sides (surface (A) and surface (B)) of the protective film. A resistivity meter (High Restor-UP, manufactured by Mitsubishi Chemical Corporation) was used as a measuring device, and measurements were performed according to JIS K 6911 under the conditions of a temperature of 20 ° C. and a relative humidity of 65%.
Further, the surface resistivity of the surface (C) and the surface (D) of the release film of the gas barrier adhesive film was measured in the same manner.

[Peeling force / charge amount]
Under the conditions of a temperature of 20 ° C. and a relative humidity of 65%, the protective film of the gas barrier adhesive film (width 50 mm, length 130 mm) is peeled off at a speed of 10 m / min using a high-speed peeling tester to increase the peeling force. It was measured.
At this time, the charge amount (±) of the exposed gas barrier layer was measured using a digital electrostatic potential measuring device (KDS-1000, manufactured by Kasuga Denki Co., Ltd.). Table 1 shows the absolute values.
Further, for the release film of the gas barrier adhesive film, the release force was measured and the charge amount of the adhesive resin layer was measured in the same manner.

[Workability evaluation]
Several A4 size gas barrier adhesive films were prepared and stacked. Then I grabbed the edge of the top gas barrier adhesive film and turned it up. At this time, the workability was evaluated by ◯ when only one of them was taken and x when the film underneath was attached.

From Table 1, the following can be seen.
In the gas barrier adhesive films (1) to (6) of Examples 1 to 6, the surface resistivity of the surface (A) is 5.0 × 10 ¹¹ Ω / □ or less, and the surface (C) or (D). The surface resistivity of is 5.0 × 10 ¹¹ Ω / □ or less. In these gas barrier adhesive films, the amount of charge after the protective film and the release film are peeled off is small.
In particular, the gas barrier adhesive films (1), (2), (4) to (6) of Examples 1, 2, 4 to 6 have the surface resistivity of at least one of the surface (B) and the surface (D). The rate is small and the workability is excellent.
On the other hand, in the gas barrier adhesive films (7) to (10) of Comparative Examples 1 to 4, the surface resistivity of the surface (A) is a large value, and the charge amount of the gas barrier layer after the protective film is peeled off is large. ..

1,12: Gas barrier adhesive film 2,13: Protective film 3,14: Gas barrier layer 4,15: Gas barrier unit 5,16: Adhesive resin layer 6,17: Release film 7,18: Adhesive unit 8: Surface (A)
9: Surface (B)
10: Surface (C)
11: Surface (D)
19: Other layers 20: Release film (1)
21a, 21b, 21c, 21d: Base film (γ)
22a, 22b, 22c, 22d: Antistatic partial layer 23a, 23b, 23c, 23d: Detachable partial layer 24: Peeling film (2)
25: Release film (3)
26: Release film (4)
27: Protective film with release film (1)
28a, 28b, 28c, 28d: Release film 29a, 29b: Antistatic adhesive partial layer 30a, 30b: Base film (α)
31: Protective film with release film (2)
32a, 32b: Base film with antistatic layer (α)
33a, 33b: Antistatic layer 34: Protective film with release film (3)
35a, 35b: Non-static adhesive partial layer 36: Protective film with release film (4)
100: Gas barrier adhesive film (1)
101: Gas barrier adhesive film (2)
102: Gas barrier adhesive film (3)
103: Gas barrier adhesive film (4)
104: Gas barrier adhesive film (5)
105: Gas barrier adhesive film (6)
106: Gas barrier adhesive film (7)
107: Gas barrier adhesive film (8)
108: Gas barrier adhesive film (9)
109: Gas barrier adhesive film (10)
110a to j: Gas barrier unit 111a to j: Adhesive unit 112a to j: Protective film 113a to j: Gas barrier layer 114a to j: Adhesive resin layer 115a to j: Release film 116a to d: Base film (α)
117a-f: Antistatic adhesive partial layer 118a-j: Base film (β)
119a to j: Gas barrier partial layer 120a to j: Detachable partial layer 121a to j: Base film (γ)
122a to l: Antistatic partial layer 123a to f: Base film with antistatic layer (α)
124a-d: Adhesive partial layer

Claims (10)

It has a gas barrier unit made of a protective film / gas barrier layer and an adhesive unit made of an adhesive resin layer / release film, and the adhesive resin layer is directly on the gas barrier layer or via another layer. It is a gas barrier adhesive film that is laminated and the protective film and the release film each form an outermost layer.
The surface resistivity of the surface of the protective film on the gas barrier layer side is 5.0 × 10 ¹¹ Ω / □ or less.
A gas barrier adhesive film having a surface resistivity of at least one of the surfaces of the release film of 5.0 × 10 ¹¹ Ω / □ or less. The gas barrier adhesive film according to claim 1, wherein the protective film is a laminated film (α) having a base film (α) and an antistatic pressure-sensitive adhesive partial layer. The gas barrier adhesive film according to claim 1 or 2, wherein the gas barrier layer is made of a laminated film (β) having a base film (β) and a gas barrier partial layer. The gas barrier adhesive film according to any one of claims 1 to 3, wherein the adhesive resin contained in the adhesive resin layer is a polyolefin-based adhesive resin. The release film is a laminated film (γ) having a base film (γ), an antistatic partial layer, and a peelable partial layer, and the peelable partial layer constitutes one of the outermost layers. The gas barrier adhesive film according to any one of 1 to 4. The gas barrier adhesive film according to any one of claims 1 to 5, which is an adhesive film for an electronic member or an optical member. The surface resistivity of the other surface of the protective film (the surface exposed to the outside in the gas barrier adhesive film) is 1.0 × 10. ⁶ Ω / □ or more 5.0 × 10 ¹¹ The gas barrier adhesive film according to any one of claims 1 to 6, which is Ω / □ or less. The surface resistivity of the surface of the release film exposed to the outside in the gas barrier adhesive film is 5.0 × 10. ¹¹ The gas barrier adhesive film according to any one of claims 1 to 7, which is Ω / □ or less. The gas barrier adhesive film according to any one of claims 1 to 8, wherein the exposed surface of the remaining laminated body is an adhesive resin layer when the release film is peeled off. An electronic member or an optical member provided with a gas barrier layer and an adhesive resin layer derived from the gas barrier adhesive film according to any one of claims 1 to 9 .

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