TW201805152A - Gas barrier film and method for producing gas barrier film - Google Patents

Abstract

The present invention relates to: a gas barrier film which comprises a base, a primer layer that is directly laminated on the base and contains a cured resin, and a gas barrier layer that is directly laminated on the primer layer, and which is characterized in that when the surface of the primer layer before the formation of the gas barrier layer is observed with an optical interferometric microscope, a smooth surface having an arithmetic mean roughness (Ra) of 4 nm or less and a maximum height of the profile (Rt) of 70 nm or less and a recessed part having a maximum profile valley depth (Rv) of 150 nm or less are observed; and a method for producing this gas barrier film. The present invention provides: a gas barrier film which comprises a base, a primer layer and a gas barrier layer and has excellent gas barrier properties and appearance; and a method for producing this gas barrier film.

Description

Gas barrier film and manufacturing method thereof

The invention relates to a gas barrier film having a substrate, a primer layer and a gas barrier layer, and having excellent gas barrier properties and appearance, and a method for manufacturing the same.

In recent years, in order to reduce the thickness, weight, and flexibility of displays such as liquid crystal displays and electroluminescence (EL) displays, substrates with electrodes have been replaced by glass substrates instead of glass plates. The so-called "gas barrier film" of the gas barrier layer.

When such a gas barrier film has fine unevenness as a transparent plastic film used as a base material, the influence of the unevenness may prevent the formation of a gas barrier layer having excellent gas barrier properties.

Therefore, an organic compound layer is provided between the gas barrier layer and the transparent plastic film.

For example, the transparent gas barrier film described in Patent Document 1 is based on at least one surface of a polyethylene substrate, and sequentially designs one or more specific organic compound layers and one or more inorganic oxide layers.

Patent Document 1 also describes that by using an organic compound layer to smooth the fine irregularities on the surface of a polyethylene substrate, a gas barrier film having excellent transparency and gas barrier properties can be obtained.

[Advanced technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2009-12310

As described in Patent Document 1, by forming an organic compound layer on a substrate, a gas barrier layer can be formed on a smoother surface, and as a result, a gas barrier film having excellent transparency and gas barrier properties can be easily obtained.

However, even when an organic compound layer is formed on a substrate, a gas barrier film having excellent gas barrier properties and appearance cannot be obtained.

This invention is made in view of the said situation, The objective is to provide the gas barrier film which has a base material, a primer layer, and a gas barrier layer, and is excellent in gas barrier property and appearance, and its manufacturing method.

In order to solve the above problems, the present inventors have conducted intensive studies on a gas barrier film having a substrate, a primer layer, and a gas barrier layer. It was found that: 1) by forming a primer layer with a specific surface state and forming a gas barrier layer thereon, a gas barrier film having excellent gas barrier properties and appearance can be obtained; and 2) such a primer layer is borrowed The method using the underlying substrate can be formed with high efficiency, and the present invention is completed.

According to the present invention, there will be provided a method for producing a gas barrier film of the following (1) to (5), and a gas barrier film of (6) and (7) below.

(1) A gas barrier film comprising: a substrate, a primer layer laminated directly on the substrate and containing a cured resin, and a gas barrier layer directly laminated on the primer layer; When the surface of the primer layer before the formation of the gas barrier layer was observed with a light interference microscope, an arithmetic mean roughness (Ra) of 4 nm or more was observed. Lower, smooth surface with a maximum cross-section height (Rt) of 70 nm or less, and recesses with a maximum valley depth (Rv) of 150 nm or less.

(2) The gas barrier film according to (1), wherein the cured resin is a cured product of an ionizing radiation-curable compound.

(3) The gas barrier film according to (1) or (2), wherein the thickness of the primer layer is 1 to 10 μm.

(4) The gas barrier film according to (1) or (2), wherein the ratio of the smooth surface is 90.00 to 99.99% of the entire surface of the primer layer.

(5) The gas barrier film according to (1) or (2), wherein the number of the recesses is an average of 1 to 500 in a square with a side length of 1 mm.

(6) A method for manufacturing a gas barrier film, which is the method for manufacturing a gas barrier film according to any one of (1) to (5), comprising the following steps 1 and 2: Step 1: a step of forming a primer layer by irradiating ionizing radiation to a laminated body of a substrate / cured resin layer / underlayer substrate layer structure; and curing the curable resin layer; and Step 2: A step of forming a gas barrier layer on the primer layer exposed by peeling the underlying substrate.

(7) The method for producing a gas barrier film according to (6), wherein a maximum vertex height (Rp) of the underlayer substrate in contact with one surface of the uncured curable resin layer is 150 nm or less.

According to the present invention, a gas barrier film having a substrate, a primer layer, and a gas barrier layer, and having excellent gas barrier properties and appearance, and a method for manufacturing the same can be provided.

The gas barrier film of the present invention comprises a substrate, a primer layer laminated directly on the substrate and containing a cured resin, and a gas barrier film laminated directly on the primer layer; When the surface of the primer layer before forming the gas barrier layer was observed with a light interference microscope, a smooth surface having an arithmetic average roughness (Ra) of 4 nm or less, a maximum cross-section height (Rt) of 50 nm or less, and a maximum valley depth (Rv) were observed. Recesses below 150nm

(Base material)

The base material constituting the gas barrier film of the present invention is not particularly limited as long as it is excellent in transparency and has sufficient strength as a base material for the gas barrier film.

The substrate is usually a resin film.

Examples of the resin component of the resin film include polyimide, polyimide, polyimide, polyphenylene ether, polyetherketone, polyetheretherketone, polyolefin, polyester, polycarbonate, Polyfluorene, polyetherfluorene, polyphenylene sulfide, acrylic resins, cycloolefin polymers, aromatic polymers, and the like.

Among these, a polyester, a polyamide, or a cyclic olefin polymer is preferable, and a polyester or a cyclic olefin polymer is more preferable from a viewpoint of being more excellent in transparency and having versatility.

Examples of the polyester system include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polyarylate. Preferably, the polyester system is polyethylene terephthalate.

Examples of the polyamide system include: fully aromatic polyamide, nylon 6, nylon 66, Nylon copolymers and so on.

烯系聚合體、單環的環狀烯烴系聚合體、環狀共軛二烯系聚合體、乙烯脂環式烴聚合體、及該等的氫化物。該具體例係可舉例如：APEL(三井化學公司製之乙烯-環烯烴共聚合體)、Arton(JSR公司製之降

烯系聚合體)、ZEONOR(日本ZEON公司製之降

烯系聚合體)等。 Examples of the cycloolefin polymer system include:

Ethylene polymers, monocyclic cyclic olefin polymers, cyclic conjugated diene polymers, ethylene alicyclic hydrocarbon polymers, and hydrides thereof. This specific example can be, for example, APEL (ethylene-cycloolefin copolymer made by Mitsui Chemicals), Arton (reduced by JSR)

Ethylene polymer), ZEONOR

Olefinic polymer) and the like.

The said resin film may contain various additives in the range which does not inhibit the effect of this invention. Examples of the additive system include an ultraviolet absorber, an antistatic agent, a stabilizer, an antioxidant, a plasticizer, a lubricant, and a coloring pigment. The content of these additives may be determined appropriately in accordance with the purpose.

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

The thickness of the substrate is not particularly limited, as long as it is determined according to the purpose of the gas barrier film. The thickness of the substrate is usually 0.5 to 500 μm, preferably 1 to 100 μm.

The arithmetic average roughness (Ra) of the substrate surface is preferably 5 to 50 nm, and more preferably 10 to 30 nm.

The maximum cross-sectional height (Rt) of the substrate surface is preferably 300 to 2000 nm or less, and more preferably 400 to 1000 nm.

By forming the surface of the substrate into the above state, a primer layer in a state described later can be formed with high efficiency.

The arithmetic average roughness (Ra) and maximum cross-section height (Rt) of the substrate surface It can be measured with a light interference microscope.

(Primer layer)

The primer layer constituting the gas barrier film of the present invention includes a layer which is directly laminated on the substrate and which contains a cured resin.

The cured resin contained in the primer layer is not particularly limited, and examples thereof include a cured product of a heat-curable compound and a cured product of an ionizing radiation-curable compound. Among these, from the viewpoint of excellent gas barrier film productivity, a cured product of an ionizing radiation-curable compound is preferred.

The ionizing radiation-curable compound is a compound having a property of being cured by irradiation with ionizing radiation, and the rest is not particularly limited, and is preferably a (meth) acrylate-based ionizing radiation-curable compound. Here, "(meth) acrylate" means "acrylate" or "methacrylate".

Examples of the (meth) acrylate-based ionizing radiation-curable compound system include (meth) acrylate-based monomers and / or prepolymers, (meth) acrylate-based resins, and the like. These systems can be used alone or in combination of two or more.

Examples of the (meth) acrylate-based monosystem include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and neopentyl glycol di ( (Meth) acrylates, neopentyl glycol adipate di (meth) acrylate, ethylene glycol di (meth) acrylate, ethylene isocyanate modified ethylene oxide di (meth) acrylate Ester, hydroxytrimethyl acetate neopentyl glycol di (meth) acrylate, dicyclopentyl di (meth) acrylate, caprolactone modified dicyclopentene di (meth) acrylate, ethylene oxide modified Difunctional (meth) acrylate compounds such as dibasic phosphoric acid di (meth) acrylate, allyl cyclohexyl di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate; Trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified Trifunctional (meth) acrylate compounds such as trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isotricyanate; diglycerol tetra (meth) acrylate, Tetrafunctional (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate; pentaerythritol penta (meth) acrylate, pentaerythritol pentaerythritol penta (meth) acrylate and other pentafunctional groups (methyl ) Acrylate compounds; hexafunctional (meth) acrylate compounds such as dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, and the like.

Examples of the (meth) acrylate resin system include amine (meth) acrylate resin, polyester (meth) acrylate resin, epoxy (meth) acrylate resin, and the like.

The urethane (meth) acrylate-based resin can be obtained by, for example, reacting a hydroxyl-containing (meth) acrylate-based compound, a polyisocyanate-based compound, and a polyol-based compound.

Examples of the hydroxyl-containing (meth) acrylate-based compounds include: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate Hydroxyalkyl (meth) acrylates such as esters, 4-hydroxybutyl (meth) acrylate, and 6-hydroxyhexyl (meth) acrylate; 2-hydroxyethyl acrylamidophosphate, phthalic acid- 2- (Meth) acryloxyethyl-2-hydroxypropyl ester, caprolactone modified 2-hydroxyethyl (meth) acrylate, dipropylene glycol (meth) acrylate, fatty acid modified-(a Based) glycidyl acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylic acid Ester, 2-hydroxy-3- (meth) acryloxypropyl (meth) acrylate, glycerol di (meth) acrylate, 2-hydroxy-3-acryloxypropyl methacrylate , Pentaerythritol tri (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexamethylene Lactone modified dipentaerythritol penta (meth) acrylate, ethylene oxide modified dipentaerythritol penta (meth) acrylate and the like.

烯二異氰酸酯、1,3-雙(異氰酸基甲基)環己烷等脂環式系聚異氰酸酯；該等聚異氰酸酯的三聚體化合物或多聚體化合物；脲基甲酸酯型聚異氰酸酯；雙縮脲型聚異氰酸酯；水分散型聚異氰酸酯(例如Nippon Polyurethane Industry(股)製的「Aquanate 100」、「Aquanate 110」、「Aquanate 200」、「Aquanate 210」等)等。 Examples of the polyisocyanate-based compound include toluene diisocyanate, diphenylmethyl diisocyanate, polyphenylmethane polyisocyanate, modified diphenylcyanate, diphenyldimethyl diisocyanate, Aromatic polyisocyanates such as tetramethyl diphenylene diisocyanate, diphenylene diisocyanate, naphthalene diisocyanate; hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, ionization Aliphatic polyisocyanates such as urethane triisocyanate; hydrogenated diphenyl methyl diisocyanate, hydrogenated diphenyl dimethyl diisocyanate, isophorone diisocyanate,

Alicyclic polyisocyanates such as alkene diisocyanate and 1,3-bis (isocyanatomethyl) cyclohexane; trimer or polymer compounds of these polyisocyanates; urethane-type polymers Isocyanates; Biuret-type polyisocyanates; Water-dispersible polyisocyanates (for example, "Aquanate 100", "Aquanate 110", "Aquanate 200", "Aquanate 210", etc., manufactured by Nippon Polyurethane Industry).

Examples of the polyhydric alcohol compound system include polyether polyols such as polyether polyols containing an alkylene structure, such as polyethylene glycol, polypropylene glycol, polybutylene glycol, polybutylene glycol, and polyhexylene glycol. Polyols such as ethylene glycol and diethylene glycol; polycarboxylic acids such as malonic acid, maleic acid, fumaric acid, and the like; and from propiolactone, β-methyl-δ-valerolactone, ε-caprolactone Polyester polyols such as reactants produced by reacting the three components of isocyclic esters; reactants of the above-mentioned polyols and phosgene, cyclic carbonates (ethylene carbonate, trimethylene carbonate, tetramethylene carbonate Esters, hexamethylene carbonates and other alkylene carbonates, etc.) ring-opening polymers such as polycarbonate-based polyols; homopolymers or copolymers with saturated hydrocarbon backbones such as ethylene, propylene, butene, and Polyolefin-based polyols such as those having a hydroxyl group at the molecular end; copolymers having a butadiene hydrocarbon backbone and polybutadiene-based polyols such as those having a hydroxyl group at the molecular end; methyl (meth) acrylate, (meth) A polymer or copolymer produced by reacting (meth) acrylate with ethyl acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc. In the molecule, there are at least two hydroxyl groups such as (meth) acrylic polyols; dimethylpolysiloxane polyols, polyphenylsiloxanes such as polysiloxanes, etc. .

Commercially available products of the urethane (meth) acrylate resin are, for example, "SHIKOH UT-4690", "SHIKOH UT-4692" (all of which are manufactured by Nippon Synthetic Chemical Co., Ltd.), and the like.

For example, the polyester (meth) acrylate resin system may be obtained by dehydration-condensation reaction of a polycarboxylic acid (anhydride) and a polyhydric alcohol to obtain a hydroxyl group of a polyester oligomer having a hydroxyl group at both ends, and using (meth) A compound obtained by esterifying acrylic acid; a compound obtained by adding an alkylene oxide to a polycarboxylic acid to obtain a terminal hydroxyl group of an oligomer; and performing esterification with (meth) acrylic acid.

Examples of the polycarboxylic acid (anhydride) used in the production of polyester (meth) acrylate resins include succinic acid (anhydride), adipic acid, maleic acid (anhydride), Itaconic acid (anhydride), trimellitic acid (anhydride), pyromellitic acid (anhydride), hexahydrophthalic acid (anhydride), phthalic acid (anhydride), isophthalic acid, terephthalic acid, and the like. Examples of the polyol system include 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, propylene glycol, dimethylol heptane, trimethylolpropane, Pentaerythritol, dipentaerythritol, etc.

The epoxy (meth) acrylate resin can be obtained by, for example, esterifying an ethylene oxide ring of a bisphenol-type epoxy resin or a phenol-type epoxy resin with a low molecular weight by reacting with a (meth) acrylic acid. Compounds.

These compounds can also be used as they are.

Among these, the (meth) acrylate resin is preferably an amine ester (meth) acrylate resin from the viewpoint of improving the adhesion between the substrate and the gas barrier layer.

The (meth) acrylate resin is preferably an oligomer. The molecular weight is preferably 100 to 10,000, more preferably 300 to 5000, and particularly good 300 to 1000.

When forming the primer layer, a thiol-based ionizing radiation-curable resin composition may be used together with the (meth) acrylate-based ionizing radiation-curable compound, or the (meth) acrylate-based ionizing radiation may be replaced. For a linear curing compound, a thiol-based ionizing radiation curing resin composition is used instead.

The thiol-based ionizing radiation-curable resin composition contains a compound having an ethylenically unsaturated group and a compound having a mercapto group. Examples of the compound having an ethylenically unsaturated group include an allyl alcohol derivative, an ester compound of acrylic acid and a polyhydric alcohol, an amine ester acrylate, and divinylbenzene. Examples of the compound system having a mercapto group include a polymercaptocarboxylic acid amido compound, an ester of a mercaptocarboxylic acid and a polyhydric alcohol, and the like. Commercially available products are, for example, "OP-1030K" (manufactured by Denki Kogyo Co., Ltd.).

The thickness of the primer layer is preferably 1 to 10 μm. By setting the thickness of the primer layer within such a range, a primer having a surface state described later can be formed efficiently. Layer, and a gas barrier film with excellent appearance can be easily obtained.

The surface of the primer layer before the gas barrier layer is formed. When observed with a light interference microscope, a smooth surface with an arithmetic average roughness (Ra) of 4 nm or less, a maximum cross-section height (Rt) of 50 nm or less, and a maximum valley depth (Rv) are observed. ) Recesses below 150 nm.

The arithmetic mean roughness (Ra) of the smooth surface is 4 nm or less, and preferably 3 nm or less. The maximum cross-sectional height (Rt) of the smooth surface is 70 nm or less, and preferably 60 nm or less.

By forming a gas barrier layer on a primer layer having a smooth surface with an arithmetic average roughness (Ra) and a maximum cross-section height (Rt) satisfying the above requirements, a gas barrier film having excellent gas barrier properties can be obtained.

The maximum valley depth (Rv) of the concave portion is 150 nm or less, and preferably 100 nm or less.

From the viewpoint of the uniformity of the primer layer, the recessed portion is an unfavorable part compared with the smooth surface described above, but it is technically difficult to form a primer layer composed of only the smooth surface. From the viewpoint of the gas barrier properties of the gas barrier film, compared with a primer layer having convex portions other than the smooth surface, or a primer layer having a maximum cross-section height (Rt) of the smooth surface exceeding 70 nm, The primer layer of the shallow concave portion is more preferable. That is, when a thinner gas barrier layer is formed on a primer layer having a convex portion, the gas barrier layer locally (part of the convex portion) generates an extremely thin portion, so that the primer layer is provided. The gas barrier properties of the gas barrier film are significantly deteriorated.

Accordingly, the primer layer constituting the gas barrier film of the present invention is basically composed of a smooth surface having excellent smoothness, and a portion where the smoothness cannot be achieved becomes a recessed portion that is not excessively deep. By setting the surface state of the primer layer to this state, the result can be Highly effective to form a primer layer with no obvious protrusions. In addition, a gas barrier film having a gas barrier layer formed on the primer layer in such a surface state has excellent gas barrier properties and appearance.

The proportion of the smooth surface is preferably 90.00-99.99% of the entire surface of the primer layer, and more preferably 95.0-99.99%.

The number of the recesses is an average of 1 to 500 in a square with a side length of 1 mm, and more preferably 10 to 300.

A gas barrier film having a primer layer having a smooth surface ratio and a number of recesses within the above range has better gas barrier properties and appearance.

The size of the recess is preferably a circle smaller than 30 μm in diameter, and more preferably a circle smaller than 15 μm in diameter.

The method for forming the primer layer having the above surface state is not particularly limited. For example, the primer layer of the cured product of the resin cured product is a cured product of the ionizing radiation curable compound can be formed according to the following steps A to C, or the following steps A 'to C'.

Step A: A coating liquid for forming a primer layer containing an ionizing radiation-curable compound is applied on a substrate to form a coating film.

Step B: When the coating film formed in step A is in an uncured state, a base substrate is superposed on the coating film to obtain a layered structure of a base material / uncured coating film / base material.

Step C: irradiate the laminated body with ionizing radiation to cure the uncured coating film to form a primer layer.

Step A ′: A coating liquid for forming a primer layer containing an ionizing radiation-curable compound is applied on a base substrate to form a coating film.

Step B ': When the coating film formed in step A' is in an uncured state, A base material was laminated on the coating film to obtain a multilayer structure of a base material / uncured coating film / base material.

Step C ′: irradiate the laminated body with ionizing radiation to cure the uncured coating film to form a primer layer.

The "substrate" refers to a substrate used in a manufacturing step to achieve a specific function. In this method, a resin film is usually used as a base material. In step B or B ', the surface of the uncured coating film is smoother by overlapping the underlying substrate on the uncured coating film. That is, in the case where the coating film is thin, the unevenness of the substrate will affect the surface of the coating film, resulting in a situation that a smooth primer layer cannot be formed, but this problem can be solved by using a base substrate.

The resin film used as a base material can be the same as the resin film used as a base material mentioned above, for example.

The thickness of the base substrate is not particularly limited, but is usually 20 to 200 μm, preferably 25 to 50 μm.

The arithmetic average roughness (Ra) of the bottom substrate in contact with one surface of the uncured coating film is usually 4 nm or less, preferably 3 nm or less.

The maximum vertex height (Rp) of the bottom substrate contacting one surface of the uncured coating film is usually 150 nm or less, preferably 100 nm or less.

In step A or A ', a coating liquid for forming a primer layer containing an ionizing radiation-curable compound is applied to a base material or a base material to form a coating film.

The coating liquid for forming a primer layer is obtained by dissolving or dispersing an ionizing radiation-curable compound, and optionally a photopolymerization initiator or other additives in an appropriate solvent.

啉基-丙烷-1-酮、4-(2-羥乙氧基)苯基-2-(羥-2-丙基)酮、2-羥-1-{4-[4-(2-羥-2-甲基-丙醯基)-苄基]苯基)-2-甲基-丙烷-1-酮等α-羥烷基苯基酮化合物；二苯基酮、對苯基二苯基酮、4,4'-二乙胺基二苯基酮、二氯二苯基酮等二苯基酮化合物；2-甲基蒽醌、2-乙基蒽醌、2-第三丁基蒽醌、2-胺基蒽醌等蒽醌化合物；2-甲基氧硫

、2-乙基氧硫

、2-氯氧硫

、2,4-二甲基氧硫

、2,4-二乙基氧硫

等氧硫

化合物；苄基二甲基縮酮、苯乙酮二甲基縮酮等二甲基縮酮化合物；對二甲胺基苯甲酸酯；寡聚[2-羥-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙酮]等等。 The photopolymerization initiator is not particularly limited, and conventionally known ones can be used. For example: 2,4,6-trimethylbenzylidene-diphenylphosphine oxide; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl Ether, benzoin isobutyl ether and other benzoin compounds; acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy Acetophenone compounds such as 2-phenylacetophenone; 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-hydroxycyclohexylphenone, 2-methyl-1- [ 4- (methylthio) phenyl] -2-

Linyl-propane-1-one, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) one, 2-hydroxy-1- {4- [4- (2-hydroxy 2-methyl-propanyl) -benzyl] phenyl) α-hydroxyalkyl phenyl ketone compounds such as 2-methyl-propane-1-one; diphenyl ketone, p-phenyl diphenyl Diphenyl ketone compounds such as ketones, 4,4'-diethylaminodiphenyl ketones, dichlorodiphenyl ketones; 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthracene Anthraquinone compounds such as quinone, 2-aminoanthraquinone; 2-methyloxysulfur

2-ethyloxysulfur

2-chlorooxysulfur

2,4-dimethyloxysulfur

2,4-diethyloxysulfur

Isosulfur

Compounds; dimethyl ketal compounds such as benzyl dimethyl ketal, acetophenone dimethyl ketal; p-dimethylamino benzoate; oligomeric [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] acetone] and the like.

The photopolymerization initiator is used in an amount of 0.1 to 7 mass%, preferably 1 to 5 mass% in the solid content of the coating liquid for forming the primer layer.

The additives include, for example, antistatic agents, stabilizers, antioxidants, plasticizers, lubricants, fillers, inorganic fillers, coloring pigments, and the like. These contents may be determined appropriately in accordance with the purpose.

Examples of the solvent to be used include: ester solvents such as ethyl acetate and propyl acetate; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; aromatic hydrocarbon solvents such as benzene and toluene; pentane and hexane Iso-saturated hydrocarbon solvents; and A mixed solvent of two or more solvents.

As a method for applying the coating liquid for forming a primer layer to a substrate, a known wet coating method can be used. For example: bar coating method, spin coating method, dipping method, roll coating, gravure coating, knife coating, air knife coating, hob coating, mold coating, screen printing method, spray coating, gravure method, etc. .

The coating film obtained in step A may be dried if necessary. The drying method may be a conventionally known drying method such as hot air drying, hot roll drying, or infrared irradiation. The heating temperature is usually in the range of 60 to 130 ° C. The heating time is usually a factor of seconds to tens of minutes.

In step B or B ', when the coating film formed in step A is in an uncured state, a base substrate or a base material is superposed on the coating film to obtain a laminated structure of a base material / uncured coating film / bottom substrate layer structure. body.

When obtaining this laminated body, it is preferable to fully apply a pressing pressure. If the laminating pressure is insufficient, there is a possibility that a primer layer having excellent smoothness cannot be formed or the appearance of the primer layer is poor.

The pressing pressure is preferably 0.1 MPa or more.

In step C, the uncured coating film is cured by irradiating the laminated body with ionizing radiation to form a primer layer.

"Ionizing radiation" refers to electromagnetic waves or charged particle rays that enable molecules to polymerize and crosslink. The ionizing radiation is generally ultraviolet rays or electron beams, preferably ultraviolet rays. As the ultraviolet source, light sources such as an ultra-high-pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a black lamp, a metal halide lamp, a microwave-excitation lamp, and a chemical lamp can be used. The luminous flux of the ionizing radiation is not particularly limited, and is usually in the range of 10 mJ / cm ² to 1,000 mJ / cm ² . The irradiation time is usually a factor of seconds to several hours, and the irradiation temperature is usually in the range of room temperature to 100 ° C.

The irradiation of the ionizing radiation may be performed from the substrate side or from the base substrate side.

After the primer layer is formed in this manner, the underlying substrate is usually peeled off, and then a gas barrier layer is formed on the exposed primer layer.

(Gas barrier layer)

The gas barrier layer constituting the gas barrier laminated body of the present invention is a layer having a characteristic (gas barrier property) of suppressing the penetration of gas such as oxygen and water vapor.

Examples of the gas barrier layer include an inorganic vapor-deposited film and a layer obtained by modifying a layer containing a polymer compound (hereinafter also referred to as a "polymer layer"). [In this case, the so-called "gas barrier layer" is not limited to Refers to the area modified by ion implantation, etc., but refers to "a polymer layer containing the modified area"] and so on.

Examples of the inorganic vapor-deposited film include vapor-deposited films of inorganic compounds and metals.

Examples of raw materials for the evaporation film of inorganic compounds include: 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; inorganic sulfides; inorganic nitrogen oxides such as silicon oxynitride; inorganic carbon oxides; inorganic nitrogen carbides; inorganic nitrogen carbon oxides.

Examples of the metal vapor-deposited film material include aluminum, magnesium, zinc, and tin.

These systems can be used alone or in combination of two or more.

Among these, an inorganic vapor-deposited film using an inorganic oxide, an inorganic nitride, or a metal as a raw material is preferable from the viewpoint of gas barrier properties, and an inorganic oxide or an inorganic film is more preferable from the viewpoint of transparency. An inorganic vapor-deposited film using nitride as a raw material.

Examples of the method for forming the inorganic vapor-deposited film include a PVD (physical vapor deposition) method such as a vacuum vapor deposition method, a sputtering method, and an ion plating method; a thermal CVD (chemical vapor deposition) method, a plasma CVD method, and a photo CVD method. CVD method.

The thickness of the inorganic vapor-deposited film varies depending on the inorganic compound used. From the viewpoint of gas barrier properties and handling properties, the thickness is preferably in the range of 50 to 300 nm, and more preferably in the range of 50 to 200 nm.

The gas barrier layer obtained by modifying the polymer layer. Examples of the polymer compounds used include silicon-containing polymer compounds such as polyorganosiloxane and polysilazane-based compounds; polyimide , Polyfluorene, polyfluorene, imine, polyphenylene ether, polyetherketone, polyetheretherketone, polyolefin, polyester, polycarbonate, polyfluorene, polyetherfluorene, polyphenylene sulfide, polyarylene Esters, acrylic resins, cycloolefin-based polymers, aromatic polymers, and the like.

These polymer compounds may be used singly or in combination of two or more kinds.

Among these, the polymer compound is preferably a silicon-containing polymer compound from the viewpoint that a gas barrier layer having more excellent gas barrier properties can be formed. Examples of the silicon-containing polymer compound system include polysilazane-based compounds, polycarbosilane-based compounds, polysilane-based compounds, and polyorganosiloxane-based compounds. Among them, a polysilazane-based compound is preferred from the viewpoint that a gas barrier layer having excellent gas barrier properties can be formed even though it is thin. By modifying the layer containing a polysilazane-based compound, a layer (silicon oxynitride layer) having oxygen, nitrogen, and silicon as main constituent atoms can be formed.

The polysilazane-based compound is a polymer compound having a repeating unit containing -Si-N-bond (silazane bond) in the molecule. Specifically, it has the formula (1):

Compounds showing repeating units. The number average molecular weight of the polysilazane-based compound used is not particularly limited, but is preferably 100 to 50,000.

In the formula (1), n represents an arbitrary natural number.

Rx, Ry, and Rz each represent an independent hydrogen atom, an unsubstituted (or substituted) alkyl group, an unsubstituted (or substituted) cycloalkyl group, an unsubstituted (or substituted) alkenyl group, Unsubstituted (or substituted) non-hydrolyzable groups such as aryl or alkylsilyl.

The alkyl group of the unsubstituted (or substituted) alkyl group may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, or third butyl. Alkyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, n-octyl and other alkyl groups having 1 to 10 carbon atoms.

The unsubstituted (or substituted) cycloalkyl cycloalkyl group may be, for example, a cycloalkyl group having 3 to 10 carbon atoms such as cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl.

Unsubstituted (or substituted) alkenyl alkenyl, for example: vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl Alkenyl groups with 2 to 10 carbon atoms.

Examples of the above-mentioned alkyl, cycloalkyl, and alkenyl substituents include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; hydroxyl group; thiol group; epoxy group; glycidyloxy group; (Meth) acrylic acid; phenyl, 4-methylphenyl, Unsubstituted (or substituted) aryl groups such as 4-chlorophenyl and the like.

The aryl group of an unsubstituted (or substituted) aryl group is, for example, an aryl group having 6 to 10 carbon atoms such as phenyl, 1-naphthyl, and 2-naphthyl.

Examples of the substituent of the aryl group include: halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; alkyl groups having 1 to 6 carbon atoms such as a methyl group and an ethyl group; and carbons such as a methoxy group and an ethoxy group. 1 to 6 alkoxy; nitro; cyano; hydroxyl; thiol; epoxy; glycidyloxy; (meth) acryloxy; phenyl, 4-methylphenyl, Unsubstituted (or substituted) aryl groups such as 4-chlorophenyl and the like.

Examples of the alkylsilyl group include trimethylsilyl, triethylsilyl, triisopropylsilyl, tri (thirdbutyl) silyl, methyldiethylsilyl, dimethylsilyl, and diethylsilyl. Base, silyl, ethylsilyl and the like.

Among these, Rx, Ry, and Rz are preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and more preferably a hydrogen atom.

The polysilazane-based compound having a repeating unit represented by the above formula (1) may be an inorganic polysilazane in which all of Rx, Ry, and Rz are hydrogen atoms, or at least one of Rx, Ry, and Rz. This is not a polysilazane which is a hydrogen atom.

Furthermore, in the present invention, a polysilazane-based compound may be a modified polysilazane. Examples of the modified polysilazane system include: Japanese Patent Laid-Open No. 62-195024, Japanese Patent Laid-Open No. 2-84437, Japanese Patent Laid-Open No. 63-81122, Japanese Patent Laid-Open No. 1-138108, and Japanese Patent Laid-Open No. 1-108108. Japanese Patent Publication No. 2-175726, Japanese Patent Application Publication No. 5-238827, Japanese Patent Application Publication No. 5-238827, Japanese Patent Application Publication No. 6-122852, Japanese Patent Application Publication No. 6-306329, Japanese Patent Application Publication No. 6-299118, Japanese Patent Application Publication No. 9- Those described in Japanese Patent Publication No. 31333, Japanese Patent Application Laid-Open No. 5-345826, Japanese Patent Application Laid-Open No. 4-63833, and the like.

Among these, polysilazane-based compounds are preferably all-hydrogen polymerizations in which all of Rx, Ry, and Rz are hydrogen atoms from the viewpoints of easiness of acquisition and formation of an ion-implanted layer having excellent gas barrier properties. Silazane.

In addition, as the polysilazane-based compound, a commercially available product that is commercially available in the form of a glass coating material or the like may be used as it is.

Polysilazane-based compounds can be used alone or in combination of two or more.

The polymer layer system may contain other components in addition to the above-mentioned polymer compound within a range that does not hinder the object of the present invention. Other components may be, for example, curing agents, anti-aging agents, light stabilizers, flame retardants, and the like.

The content of the polymer compound in the polymer layer is preferably 50% by mass or more and more preferably 70% by mass or more from the viewpoint of obtaining a gas barrier layer having more excellent gas barrier properties.

The thickness of the polymer layer is not particularly limited, but is preferably in the range of 50 to 300 nm, and more preferably in the range of 50 to 200 nm.

In the present invention, even if the thickness of the polymer layer is in the order of nanometers, a gas-barrier laminate having sufficient gas-barrier properties can be obtained.

The method for forming the polymer layer is not particularly limited. For example, a polymer layer-forming solution containing at least one of the polymer compounds, other components as needed, and a solvent is prepared, and then the polymer layer-forming solution is applied by a known method, and the obtained coating is applied. The film is dried to form a polymer layer.

Examples of the solvent used for the solution for forming a polymer layer include aromatic hydrocarbon solvents such as benzene and toluene; and ester systems such as ethyl acetate and butyl acetate. Solvents; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone; aliphatic hydrocarbon solvents such as n-pentane, n-hexane, and n-heptane; alicyclic hydrocarbon solvents such as cyclopentane, cyclohexane, and the like.

These solvents may be used alone or in combination of two or more.

The coating method of the polymer layer forming solution may be, for example, a bar coating method, a spin coating method, a dipping method, a roll coating method, a gravure coating method, a knife coating method, an air knife coating method, a roll knife coating method, or a die coating method. Cloth, screen printing, spraying, gravure and so on.

A method for drying the formed coating film is a conventionally known drying method such as hot air drying, hot roll drying, or infrared irradiation. The heating temperature is usually in the range of 60 to 130 ° C. The heating time is usually a factor of seconds to tens of minutes.

Examples of the modification treatment of the polymer layer include ion implantation treatment, plasma treatment, ultraviolet irradiation treatment, and heat treatment.

The ion implantation process is a method of implanting ions into a polymer layer and modifying the polymer layer as described later.

Plasma treatment is a method of modifying a polymer layer by exposing the polymer layer to a plasma. For example, plasma processing can be performed according to the method described in Japanese Patent Laid-Open No. 2012-106421.

The ultraviolet irradiation treatment is a method of modifying the polymer layer by irradiating the polymer layer with ultraviolet rays. For example, according to the method described in Japanese Patent Laid-Open Publication No. 2013-226757, ultraviolet light modification treatment can be performed.

Among these, from the viewpoints that the surface of the polymer layer is not rough, it is modified to the inside with high efficiency, and a gas barrier layer having more excellent gas barrier properties can be formed, and is preferably an ion implantation process.

Examples of the ion system implanted in the polymer layer include: ions of rare gases such as argon, helium, neon, krypton, and xenon; ions of fluorocarbons, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, and sulfur; methane Ions of alkane-based gases such as ethane and ethane; Ions of olefin-based gases such as ethylene and propylene; Ions of diene-based gases such as pentadiene and butadiene; Ions of acetylene-based gases such as acetylene; benzene and toluene Ions such as aromatic hydrocarbon-based gases; cyclic alkane-based gases such as cyclopropane; cyclic olefin-based gases such as cyclopentene; ions of metals; ions of organic silicon compounds and the like.

These ion systems can be used individually by 1 type or in combination of 2 or more types.

Among these, from the viewpoint that ions can be more easily implanted and a gas barrier layer having more excellent gas barrier properties can be formed, ions of a rare gas such as argon, helium, neon, krypton, and xenon are preferred.

The implantation amount of ions can be appropriately determined in accordance with the purpose of use of the gas-barrier laminated body (necessary gas-barrier properties, transparency, etc.).

Examples of the method of implanting ions include a method of irradiating ions (ion beams) using an electric field, and a method of implanting ions in a plasma. Among them, from the viewpoint that the target barrier layer can be easily obtained, the present invention is preferably the latter plasma ion implantation method.

Plasma ion implantation is the generation of plasma in an environment containing plasma-generating gas such as a rare gas. By applying a negative voltage pulse to a polymer layer, ions (cations) in the plasma can be implanted. On the surface of the polymer layer.

The thickness of the implanted ion area by ion implantation can be controlled according to the implantation conditions such as the type of ions, applied voltage, and processing time, as long as it is matched with the thickness of the polymer layer and the purpose of the laminate. can, Usually 10 ~ 300nm.

The gas barrier film of the present invention is excellent in both gas barrier properties and appearance.

When the gas barrier film of the present invention measures the water vapor transmission rate by the method described in the examples, it is usually 1 × 10 ^-3 g / (m ² ‧day) or less.

The gas barrier film of the present invention is suitable for display parts such as a liquid crystal display, an EL display, and the like because of the above characteristics.

An electronic device according to the present invention includes the electronic device component according to the present invention. Specific examples include liquid crystal displays, organic EL displays, inorganic EL displays, electronic paper, and solar cells.

Since the electronic device of the present invention is provided with parts for electronic devices composed of the gas barrier film of the present invention, it has excellent gas barrier properties.

(Manufacturing method of gas barrier film)

The gas barrier film of the present invention can be manufactured efficiently, for example, by using a method for manufacturing a gas barrier film including the following steps 1 and 2.

Step 1: A step of forming a primer layer by applying ionizing radiation to a laminate of a substrate / cured resin layer / underlayer substrate layer structure to cure the curable resin layer.

Step 2: The step of peeling the underlying substrate to form a gas barrier layer on the exposed primer layer

In step 1, a laminated body (hereinafter also referred to as a "laminated body (α)") having a structure of a base material / an uncured curable resin layer / an underlying base material layer structure is prepared.

The layered body (α) is the same as the layered body (ie, the layered body of the substrate / uncured coating film / bottom substrate layer structure) obtained in accordance with the step B exemplified in the primer layer forming method.

Therefore, the base material constituting the laminated body (α) finally becomes the base material of the gas barrier film of the present invention, and the uncured curable resin layer constituting the laminated body (α) becomes the bottom of the gas barrier film of the present invention after curing. Paint layer.

In step 1, the production of the laminated body (α) and the curing of the curable resin layer can be performed according to the method described above.

In step 2, the base substrate is peeled off to form a gas barrier layer on the exposed primer layer.

The formation of the gas barrier layer can be performed according to the method described above.

According to the method of the present invention, the gas barrier film of the present invention can be formed with high efficiency.

[Example]

Hereinafter, the present invention will be described in more detail with examples. However, the present invention is not limited to the following examples.

The "parts" and "%" in each case are the basis of quality without a special statement.

[Surface observation]

In the examples and comparative examples, the surface observation of the substrate and the primer layer formed was performed using a light interference microscope for a region with a side length of 1 mm.

[Manufacturing Example 1] Preparation of primer layer-forming solution A

After dissolving 20 parts of tricyclodecane dimethanol diacrylate (manufactured by Shin Nakamura Chemical Co., Ltd., "A-DCP") in 100 parts of methyl isobutyl ketone, a photopolymerization initiator (manufactured by BASF Co., Ltd., " Irgacure 127 ″) 3 parts to prepare a primer layer forming solution A (solid content ratio 20%).

[Manufacturing Example 2] Preparation of primer layer-forming solution B

Polyurethane acrylate UV-curable resin compound (Toyobo "VYLON® UR 1350" manufactured by the company) was dissolved in methyl isobutyl ketone to prepare solution B for forming a primer layer (solid content ratio: 20%).

[Example 1]

The above-mentioned primer layer-forming solution A was applied to a polyethylene terephthalate (PET) film (manufactured by Mitsubishi Resin Corporation, "PET25 T600E") with a thickness of 25 μm, and the obtained coating film was applied. Heat and dry at 70 ° C for 1 minute. A single-sided undercoating PET film ("PET50A4100", manufactured by Toyobo Co., Ltd., with a thickness of 50 µm) was used as a smooth base substrate, and one side of the smooth base substrate that had not been primed was laminated to the uncured coating. On the film, a laminate was obtained.

Using a conveyor-type UV light irradiation device (manufactured by Fusion, "F600V", UV lamp: high-pressure mercury lamp, linear speed: 20m / min, integrated luminous flux: 120mJ / cm ² , illuminance 1.466W, lamp height: 104mm), The laminated body was irradiated twice with ultraviolet (UV light) to form a primer layer having a thickness of 2 μm.

Peel off the underlying substrate, and apply perhydropolysilazane (Clariant, "AQUAMICA NL110A-20") to the exposed primer layer by spin coating, and then apply the obtained coating film at 120 ° C for 2 minutes Heating to form a polymer layer. The plasma ion implantation method is used to implant argon ions into the surface of the polymer layer to form a gas barrier layer, thereby preparing a gas barrier film.

The plasma ion implantation device and ion implantation conditions used to form the gas barrier layer are as follows:

(Plasma ion implantation device)

RF power supply: Model "RF" 56000 made by Japan Electronics Co., Ltd.

High-voltage pulse power supply: "PV-3-HSHV-0835" manufactured by Kurita Manufacturing Co., Ltd.

(Plasma ion implantation conditions)

Plasma generated gas: Ar

Gas flow: 100sccm

Duty ratio: 0.5%

Applied voltage: -6kV

RF power supply: 13.56MHz frequency, 1000W applied power

Amine internal pressure: 0.2Pa

Pulse width: 5μsec

Processing time (ion implantation time): 200 seconds

[Example 2]

A gas barrier film was obtained in the same manner as in Example 1 except that the thickness of the primer layer was changed to 5 μm.

[Example 3]

In Example 1, a gas barrier film was obtained in the same manner as in Example 1 except that the thickness of the primer layer was changed to 10 μm.

[Example 4]

A gas barrier film was obtained in the same manner as in Example 1 except that the primer layer was formed using the primer layer forming solution B.

[Example 5]

In Example 1, a gas barrier film was obtained in the same manner as in Example 1 except that a 50 μm-thick polycarbonate film ("PUREACE® S-148" manufactured by Teijin Kasei Co., Ltd.) was used as the base material.

[Comparative Example 1]

In Example 1, a gas barrier film was obtained in the same manner as in Example 1 except that UV light irradiation was performed without laminating the base substrate.

For the gas barrier films obtained in the examples and comparative examples, appearance observation and measurement of water vapor transmission rate were performed as follows. The results are shown in Table 1.

[Appearance observation]

The gas barrier film was visually observed, and those who observed full air intrusion were rated "×", others were rated "○".

[Determination of water vapor transmission rate]

The water vapor transmission rate of the gas barrier film was measured using a water vapor measuring device (manufactured by Mocon Corporation, "AQUATRAN-1"). The measurement is at 40. C. Implemented under 90% relative humidity. Those with a water vapor transmission rate exceeding 1 × 10 ^-1 g / (m ² ‧day) are rated as “×”, and those with a water vapor transmission rate of 1 × 10 ^-1 g / (m ² ‧day) or less are more than 1 × 10 ^-3 Those with g / (m ² ‧day) were rated as "△", and those with less than 1 × 10 ^-3 g / (m ² ‧day) were rated as "○".

The following items are known from Table 1.

The gas barrier films of Examples 1 to 5 were excellent in gas barrier properties and appearance. On the other hand, the gas barrier film of Comparative Example 1 cannot be used because the surface of the primer layer is rough. A gas barrier layer having excellent gas barrier properties is formed, which exhibits poor gas barrier properties.

Claims (7)

A gas barrier film, comprising: a substrate, a primer layer laminated directly on the substrate and containing a cured resin, and a gas barrier layer directly laminated on the primer layer; When the surface of the primer layer in front of the layer was observed with a light interference microscope, smooth surfaces with an arithmetic average roughness (Ra) of 4 nm or less, a maximum cross-section height (Rt) of 70 nm or less, and recesses with a maximum valley depth (Rv) of 150 nm or less were observed. . For example, the gas barrier film according to item 1 of the application, wherein the cured resin is a cured product of an ionizing radiation-curable compound. For example, the gas barrier film according to item 1 or 2 of the patent scope, wherein the thickness of the primer layer is 1 to 10 μm. For example, the gas barrier film according to item 1 or 2 of the scope of patent application, wherein the proportion of the smooth surface is 90.00-99.99% of the entire surface of the primer layer. For example, the number of the gas-barrier films in the range of 1 or 2 of the patent application, wherein the number of the above-mentioned recesses is an average of 1 to 500 in a square with a side length of 1 mm. A method for manufacturing a gas barrier film, which is a method for manufacturing a gas barrier film according to any one of claims 1 to 5, includes the following steps 1 and 2: Step 1: By the substrate / uncured state A step of curing the curable resin layer to form a primer layer by irradiating ionizing radiation to the laminated body of the curable resin layer / substrate substrate layer structure; and step 2: on the primer layer exposed by peeling the primer substrate , The step of forming a gas barrier layer. For example, the method for manufacturing a gas barrier film according to item 6 of the patent application, wherein the maximum vertex height (Rp) of the above-mentioned base substrate contacting one surface of the uncured curable resin layer is 150 nm or less.