JP2011000718A - Gas-barrier film and member for electronic devices - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas-barrier film which can be manufactured simply at low cost and is superior in adhesion, surface smoothness, gas-barrier properties, and transparency and a member for electronic devices made of the gas-barrier film.SOLUTION: The gas-barrier film has a layer which is obtained by injecting ions in a polymer layer through a primer layer on at least one side of a base material film. The member for electronic devices is made of the gas-barrier film.

Description

  The present invention relates to a gas barrier film excellent in interlayer adhesion and smoothness, and an electronic device member comprising the gas barrier film.

In recent years, it has been attempted to manufacture a flexible display using a synthetic resin sheet instead of a glass substrate in an image display device. However, the synthetic resin sheet has problems such as easier permeation of gas such as water vapor and lower surface smoothness than glass, and has many problems in practical use.
In order to solve such problems, Patent Documents 1 and 2 propose a gas barrier sheet in which a smooth layer is provided on a synthetic resin sheet and a gas barrier inorganic compound thin film is laminated (Patent Documents 1, 2). 2).
However, the gas barrier sheet described in these documents has poor adhesion between the smooth layer and the inorganic material layer serving as the gas barrier layer or electrode material, and three layers of functional thin films are provided between the layers to increase the adhesion. It has to be provided, and the increase in the thickness of the resulting gas barrier sheet and the number of steps associated therewith have been problems.

JP 2003-154596 A JP 2006-264118 A

  The present invention has been made in view of the above-described conventional technology, and can be manufactured easily and at low cost, and includes a gas barrier film excellent in adhesion, surface smoothness, gas barrier properties, and transparency, and the gas barrier film. It is an object to provide a member for an electronic device.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have provided a gas barrier film in which a layer (gas barrier layer) obtained by implanting ions into a polymer layer is provided on at least one surface side of a base film. The present inventors have found that a gas barrier film having excellent interlayer adhesion and surface smoothness can be obtained by providing a primer layer between the base film and the gas barrier layer, and the present invention has been completed.

Thus, according to the first aspect of the present invention, the following gas barrier films (1) to (6) are provided.
(1) A gas barrier film comprising a layer obtained by implanting ions into a polymer layer via a primer layer on at least one surface side of a base film.
(2) The gas barrier film according to (1), wherein the polymer layer is a layer containing a silicon-based polymer compound.
(3) The gas barrier film according to (1) or (2), wherein the primer layer comprises a silicon-containing compound.
(4) The primer layer is formed of at least one silicon-containing compound selected from the group consisting of polysilicate, polysilazane, polycarbosilane, polysilane, and silane coupling agent (1) The gas barrier film according to any one of to (3).
(5) The gas barrier film according to any one of (1) to (4), wherein the layer containing a silicon-based compound has a layer obtained by implanting ions by a plasma ion implantation method.
(6) The gas barrier film according to any one of (1) to (5), wherein the water vapor transmission rate under an atmosphere of 40 ° C. and a relative humidity of 90% is less than 0.5 g / m ² / day. .

According to the second aspect of the present invention, the following electronic device member (7) is provided.
(7) A member for an electronic device comprising the gas barrier film according to any one of (1) to (6).

The gas barrier film of the present invention is extremely excellent in interlayer adhesion and surface smoothness, and also excellent in gas barrier properties and transparency.
Therefore, the gas barrier film of the present invention can be suitably used as a packaging material such as food and medicine, a member for an electronic device such as a flexible display and a solar cell (for example, a solar cell back sheet).

It is a figure which shows schematic structure of the plasma ion implantation apparatus used for this invention. It is a figure which shows schematic structure of the plasma ion implantation apparatus used for this invention. It is an electron micrograph after the crosscut test of Example 1 of the present invention. It is an electron micrograph after the crosscut test of the comparative example 3 of this invention.

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

1) Gas barrier film The gas barrier film of the present invention (hereinafter also referred to as “the film of the present invention”) has ions implanted into a polymer layer via a primer layer on at least one surface side of a base film. It has the layer obtained by being manufactured.

(Base film)
The material for the base film used in the present invention is not particularly limited as long as it can support the primer layer and the polymer layer. The material of the base film is polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, acrylic resin, A cycloolefin type polymer, an aromatic polymer, etc. are mentioned.

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

Examples of the polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polyarylate.
Examples of the polyamide include wholly aromatic polyamide, nylon 6, nylon 66, nylon copolymer, and the like.

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

(Primer layer)
The film of the present invention is characterized by having a primer layer between a base film and a layer obtained by implanting ions into a polymer layer (hereinafter sometimes referred to as “gas barrier layer”). .
A primer layer plays the role which improves the interlayer adhesiveness of a base film and a gas barrier layer.
By providing the primer layer, it is possible to obtain a gas barrier film that is extremely excellent in interlayer adhesion and surface smoothness.

  It does not specifically limit as a material which comprises a primer layer, A well-known thing can be used. For example, a photopolymerizable composition comprising a silicon-containing compound; a photopolymerizable compound comprising a photopolymerizable monomer and / or a photopolymerizable prepolymer, and a polymerization initiator that generates radicals at least in the visible light region; Resin, polyurethane resin (especially two-part curable resin of polyacryl polyol, polyester polyol, polyether polyol, etc. and isocyanate compound), acrylic resin, polycarbonate resin, vinyl chloride / vinyl acetate copolymer, polyvinyl butyral Resins such as resins and nitrocellulose resins; alkyl titanates; ethyleneimines; These materials can be used alone or in combination of two or more.

  Among these, as will be described later, when the polymer layer is a layer containing a silicon-based polymer compound, a silicon-containing compound is preferable because better interlayer adhesion and surface smoothness can be obtained.

  Examples of the silicon-containing compound include at least one selected from the group consisting of polysilicate; silane coupling agent; polysilazane; polycarbosilane; polysilane.

Examples of the polysilicate include alkyl polysilicates such as methyl polysilicate which is a partial hydrolysis condensate of tetramethoxysilane and ethyl polysilicate which is a partial hydrolysis condensate of tetraethoxysilane; formula: M ₂ O · nSiO ₂ (formula M represents an alkali metal atom such as lithium or sodium, and n represents a positive number of 2 to 10).

  Examples of silane coupling agents include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, and 3- (2-aminoethyl) aminopropyltriethoxysilane. , 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldiethoxysilane, and other aminosilane coupling agents; 3-glycidoxypropyltrimethoxysilane, 3-glycid Epoxy silane coupling agents such as xyloxymethyldimethoxysilane; 3-mercaptopropyltrimethoxysilane; 3-methacryloxypropyltrimethoxysilane; JP 2000-239447 A, JP 2001-40037 A, etc. Molecular silane coupling agent; and the like.

  Examples of polysilazane, polycarbosilane, and polysilane include those similar to polysilazane, polycarbosilane, and polysilane used as a material for forming a polymer layer described later.

  For the primer layer, a primer layer forming solution obtained by dissolving or dispersing the material constituting the primer layer in an appropriate solvent is applied to one or both sides of the base film, and the obtained coating film is dried to obtain a desired layer. It can form by heating by.

  As a method for applying the primer layer forming solution to the substrate film, a normal wet coating method can be used. Examples include dipping method, roll coating, gravure coating, knife coating, air knife coating, roll knife coating, die coating, screen printing method, spray coating, gravure offset method and the like.

As a method for drying the coating film of the primer layer forming solution, conventionally known drying methods such as hot air drying, hot roll drying, and infrared irradiation can be employed.
The thickness of the primer layer is usually 10 to 1000 nm.

  Alternatively, the obtained primer layer may be ion-implanted by a method similar to the method of ion-implanting the polymer layer described later, and then the polymer layer may be formed. By performing ion implantation also on the primer layer, a more excellent gas barrier film can be obtained.

(Polymer layer)
Examples of the polymer compound constituting the polymer layer include silicon-based polymer compounds, polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polysulfone, and polyether. Examples include sulfone, polyphenylene sulfide, polyarylate, acrylic resin, cycloolefin polymer, aromatic polymer, and combinations of two or more of these polymers.

The polymer compound may be a cured product of an energy ray curable compound. Examples of energy ray curable compounds include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neo Pentyl glycol adipate di (meth) acrylate, dicyclopentanyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) ) Acrylate, tris (acryloxyethyl) isocyanurate, dipentaerythritol hexa (meth) acrylate and other polyfunctional acrylates such as polyfunctional acrylate energy ray polymerizable monomers; polyester (meth) acrylate Epoxy (meth) acrylate, urethane (meth) acrylate, polyol (meth) acrylate, multifunctional acrylate oligomer and silicone (meth) acrylate; and the like. Here, (meth) acrylate means acrylate or methacrylate.
Among these, a silicon-based polymer compound is preferably used from the viewpoint of water vapor permeability, adhesion, and transparency.

  The silicon-based polymer compound may be an organic compound or an inorganic compound as long as it is a silicon-containing polymer. Examples include polyorganosiloxane compounds, polycarbosilane compounds, polysilane compounds, polysilazane compounds, and the like.

  A polyorganosiloxane compound is a compound obtained by polycondensation of a silane compound having a hydrolyzable functional group.

There is no restriction | limiting in the principal chain structure of a polyorganosiloxane type compound, Any of linear shape, ladder shape, and bowl shape may be sufficient.
For example, the linear main chain structure is a structure represented by the following formula (a), and the ladder main chain structure is a structure represented by the following formula (b): a cage main chain structure And the structure represented by the following formula (c).

  In the formula, each of Rx, Ry, and Rz independently represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group, etc. Represents a hydrolyzable group. Note that the plurality of Rx in the formula (a), the plurality of Ry in the formula (b), and the plurality of Rz in the formula (c) may be the same or different. However, both Rx in the formula (a) are not hydrogen atoms.

  Examples of the alkyl group of the unsubstituted or substituted alkyl group include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n Examples thereof include alkyl groups having 1 to 10 carbon atoms such as a pentyl group, an isopentyl group, a neopentyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group.

  As an alkenyl group, C2-C10 alkenyl groups, such as a vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, are mentioned, for example.

  Examples of the substituent for the alkyl 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 unsubstituted or substituted aryl group such as a 4-methylphenyl group and a 4-chlorophenyl group;

  Examples of the aryl group of the unsubstituted or substituted aryl group include aryl groups having 6 to 10 carbon atoms such as a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

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

  Among these, as Rx, Ry, and Rz, a hydrogen atom, a C1-C6 alkyl group, or a phenyl group is preferable, and a C1-C6 alkyl group is especially preferable.

  As the polyorganosiloxane-based compound, a linear compound represented by the above formula (a) is preferable. From the viewpoint of easy availability and formation of a layer having excellent gas barrier properties, 2 in the above formula (a). Polydimethylsiloxane in which two Rx are both methyl group compounds is more preferable.

  The polyorganosiloxane compound can be obtained, for example, by a known production method in which a silane compound having a hydrolyzable functional group is polycondensed.

  What is necessary is just to select the silane compound to be used suitably according to the structure of the target polyorganosiloxane type compound. Preferred examples include bifunctional silane compounds such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, and diethyldiethoxysilane; methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, trifunctional silane compounds such as n-propyltrimethoxysilane, n-butyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyldiethoxymethoxysilane; tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, Tetraisopropoxysilane, tetra-n-butoxysilane, tetra-t-butoxysilane, tetra-s-butoxysilane, methoxytriethoxysilane, dimethoxydiethoxysilane, tri Butoxy, etc. tetrafunctional silane compounds such as tetraethoxysilane and the like.

  The polycarbosilane compound is a polymer compound having a (—Si—C—) bond in the main chain in the molecule. Especially, as a polycarbosilane type compound used for this invention, what contains the repeating unit represented by following formula (d) is preferable.

  In the formula, Rw and Rv each independently represent a hydrogen atom, a hydroxyl group, an alkyl group, an aryl group, an alkenyl group, or a monovalent heterocyclic group. A plurality of Rw and Rv may be the same or different.

  Examples of the alkyl group, aryl group, and alkenyl group for Rw and Rv include the same groups as those exemplified as Rx and the like.

The heterocyclic ring of the monovalent heterocyclic group is not particularly limited as long as it is a 3- to 10-membered cyclic compound containing at least one hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom in addition to a carbon atom.
Specific examples of the monovalent heterocyclic group include 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-thienyl group, 3-thienyl group, 2-furyl group, 3-furyl group, and 3-pyrazolyl. Group, 4-pyrazolyl group, 2-imidazolyl group, 4-imidazolyl group, 1,2,4-triazin-3-yl group, 1,2,4-triazin-5-yl group, 2-pyrimidyl group, 4- Pyrimidyl group, 5-pyrimidyl group, 3-pyridazyl group, 4-pyridazyl group, 2-pyrazyl group, 2- (1,3,5-triazyl) group, 3- (1,2,4-triazyl) group, 6 -(1,2,4-triazyl) group, 2-thiazolyl group, 5-thiazolyl group, 3-isothiazolyl group, 5-isothiazolyl group, 2- (1,3,4-thiadiazolyl) group, 3- (1, 2,4-thiadiazolyl) group, 2-oxazoly Group, 4-oxazolyl group, 3-isoxazolyl group, 5-isoxazolyl group, 2- (1,3,4-oxadiazolyl) group, 3- (1,2,4-oxadiazolyl) group, 5- (1,2, 3-oxadiazolyl) group and the like.

  These groups may have a substituent such as an alkyl group, an aryl group, an alkoxy group, or an aryloxy group at an arbitrary position.

R represents an alkylene group, an arylene group or a divalent heterocyclic group.
Examples of the alkylene group of R include alkylene groups having 1 to 10 carbon atoms such as a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, and an octamethylene group.

  Examples of the arylene group include arylene groups having 6 to 20 carbon atoms such as a phenylene group, a 1,4-naphthylene group, and a 2,5-naphthylene group.

  As the divalent heterocyclic group, a divalent group derived from a 3 to 10-membered heterocyclic compound containing at least one hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom in addition to a carbon atom is particularly preferable. There are no restrictions.

  Specific examples of the divalent heterocyclic group include thiophenediyl groups such as 2,5-thiophenediyl group; flangedyl groups such as 2,5-furandiyl group; and selenophene such as 2,5-selenophenediyl group. Diyl group; pyrrole diyl group such as 2,5-pyrrole diyl group; pyridinediyl group such as 2,5-pyridinediyl group and 2,6-pyridinediyl group; 2,5-thieno [3,2-b] thiophenediyl group , 2,5-thieno [2,3-b] thiophenediyl groups, etc .; quinolinediyl groups, such as 2,6-quinolinediyl groups; 1,4-isoquinolinediyl groups, 1,5-isoquinolinediyl groups, etc. Isoquinolinediyl group of quinoxalinediyl group such as 5,8-quinoxalinediyl group; benzo [4,7-benzo [1,2,5] thiadiazolediyl group , 2,5] thiadiazole diyl group; benzothiazole diyl group such as 4,7-benzothiazole diyl group; carbazole diyl group such as 2,7-carbazole diyl group and 3,6-carbazole diyl group; 3,7-phenoxy A phenoxazinediyl group such as a sazinediyl group; a phenothiazinediyl group such as a 3,7-phenothiazinediyl group; a dibenzosiloldiyl group such as a 2,7-dibenzosiloldiyl group; 2,6-benzo [1,2-b: 4,5-b ′] dithiophenediyl group, 2,6-benzo [1,2-b: 5,4-b ′] dithiophenediyl group, 2,6-benzo [2,1-b: 3, Benzodithiophene diyl groups such as 4-b ′] dithiophene diyl group and 2,6-benzo [1,2-b: 3,4-b ′] dithiophene diyl group.

  The alkylene group, arylene group, and divalent heterocyclic group represented by R may have a substituent such as an alkyl group, an aryl group, an alkoxy group, or a halogen atom at an arbitrary position.

  Among these, in formula (1), Rw and Rv are each independently a hydrogen atom, an alkyl group or an aryl group, and more preferably include a repeating unit in which R is an alkylene group or an arylene group, Rw, More preferably, each Rv independently represents a hydrogen atom or an alkyl group, and R includes an alkylene group.

  The weight average molecular weight of the polycarbosilane compound having a repeating unit represented by the formula (d) is usually 400 to 12,000.

  It does not specifically limit as a manufacturing method of a polycarbosilane type compound, A conventionally well-known method is employable. For example, a method for producing by thermal decomposition polymerization of polysilane (Japanese Patent Laid-Open No. 51-126300), a method for producing by thermal rearrangement of poly (dimethylsilane) (Journal of Materials Science, 2569-2576, Vol. 13, 1978). , A method for obtaining a polycarbosilane compound by Grignard reaction of chloromethyltrichlorosilane (Organometallics, 1336-1344, Vol. 10, 1991), a method for producing by ring-opening polymerization of disilacyclobutanes (Journal of Organometallic Chemistry, 1 -10, Vol. 521, 1996), a raw material polymer having a structural unit of dimethylcarbosilane and SiH group-containing silane, water and / or in the presence of a basic catalyst. A method of producing by reacting rucol (Japanese Patent Laid-Open No. 2006-117717), carbosilane having an organometallic group such as trimethyltin at the terminal is polymerized with an organic typical metal compound such as n-butyllithium as an initiator. And a manufacturing method (Japanese Patent Laid-Open No. 2001-328991).

  The polysilane-based compound is a polymer compound having a (—Si—Si—) bond in the molecule. Examples of such polysilane compounds include compounds having at least one repeating unit selected from structural units represented by the following formula (e).

  In the formula (e), Rq and Rr are the same or different and are a hydrogen atom, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, a hydroxyl group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group. A group, an amino group optionally having a substituent, a silyl group, or a halogen atom is represented.

  Examples of the alkyl group, alkenyl group, and aryl group of Rq and Rr include the same as those exemplified for Rx and the like.

Examples of the cycloalkyl group include cycloalkenyl groups having 3 to 10 carbon atoms such as a cyclopentyl group, a cyclohexyl group, and a methylcyclohexyl group.
As a cycloalkenyl group, C4-C10 cycloalkenyl groups, such as a cyclopentenyl group and a cyclohexenyl group, are mentioned.

As an alkoxy group, C1-C10 alkoxy groups, such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, t-butoxy group, a pentyloxy group, are mentioned.
Examples of the cycloalkyloxy group include cycloalkyloxy groups having 3 to 10 carbon atoms such as a cyclopentyloxy group and a cyclohexyloxy group.

Examples of the aryloxy group include aryloxy groups having 6 to 20 carbon atoms such as a phenoxy group and a naphthyloxy group.
Examples of the aralkyloxy group include aralkyloxy groups having 7 to 20 carbon atoms such as benzyloxy group, phenethyloxy group, and phenylpropyloxy group.
The amino group which may have a substituent is an amino group; an N-mono or N, N-disubstituted amino group substituted with an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an acyl group, or the like. Is mentioned.

As the silyl group, a Si _1-10 silanyl group (preferably Si _1-6 silanyl group) such as a silyl group, a disilanyl group, or a trisilanyl group, a substituted silyl group (for example, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group) , Substituted silyl groups substituted with alkoxy groups, etc.).
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  The cycloalkyl group, cycloalkenyl group, alkoxy group, cycloalkyloxy group, aryloxy group, aralkyloxy group, silyl group may have a substituent such as a halogen atom, an alkyl group, an aryl group, or an alkoxy group. Good.

  Among these, since the more excellent effect of the present invention is obtained, a compound containing a repeating unit represented by the formula (e) is preferable. In the formula (e), Rq and Rr are each independently A compound containing a repeating unit which is a hydrogen atom, a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, an amino group or a silyl group is more preferable. In the formula (e), Rq and Rr are each independently a hydrogen atom, More preferred are compounds containing a repeating unit which is an alkyl group or an aryl group.

The form of the polysilane compound is not particularly limited, and may be a random copolymer, a block even if it is a homopolymer such as acyclic polysilane (linear polysilane, branched polysilane, network polysilane, etc.) or cyclic polysilane. Copolymers such as copolymers, alternating copolymers, and comb copolymers may also be used.
When the polysilane compound is an acyclic polysilane, the terminal group (terminal substituent) of the polysilane compound is a hydrogen atom, a halogen atom (chlorine atom, etc.), an alkyl group, a hydroxyl group, an alkoxy group, silyl It may be a group or the like.

  Specific examples of the polysilane compound include polydialkylsilanes such as polydimethylsilane, poly (methylpropylsilane), poly (methylbutylsilane), poly (methylpentylsilane), poly (dibutylsilane), and poly (dihexylsilane). , Homopolymers such as poly (diarylsilanes) such as poly (diphenylsilane), poly (alkylarylsilanes) such as poly (methylphenylsilane); dialkylsilanes such as dimethylsilane-methylhexylsilane copolymers and other dialkylsilanes Copolymer, arylsilane-alkylarylsilane copolymer such as phenylsilane-methylphenylsilane copolymer, dimethylsilane-methylphenylsilane copolymer, dimethylsilane-phenylhexylsilane copolymer, dimethylsilane-methylnaphthy And the like; silane copolymer, methyl propyl silane - copolymers of alkyl aryl silane copolymer - dialkyl silane and methyl phenyl silane copolymer.

  For details on the polysilane compound, see, for example, R.I. D. Miller, J.M. Michl; Chemical Review, 89, 1359 (1989); Matsumoto; Japan Journal of Physics, Vol. 37, p. 5425 (1998). In the present invention, polysilane compounds described in these documents can be used.

The average degree of polymerization (for example, the number average degree of polymerization) of the polysilane compound is generally about 5 to 400, preferably about 10 to 350, and more preferably about 20 to 300.
The weight average molecular weight of the polysilane compound is about 300 to 100,000, preferably about 400 to 50,000, and more preferably about 500 to 30,000.

  Many of the polysilane compounds are known substances and can be produced using known methods. For example, a method of dehalogenating polycondensation of halosilanes using magnesium as a reducing agent (“magnesium reduction method”, WO 98/29476, etc.), a method of dehalogenating polycondensation of halosilanes in the presence of an alkali metal (“kipping method”). J. Am. Chem. Soc., 110, 124 (1988), Macromolecules, 23, 3423 (1990), etc.], a method of dehalogenating polycondensation of halosilanes by electrode reduction (J. Chem. Soc., Chem.). Commun., 1161 (1990), J. Chem. Soc., Chem. Commun. 897 (1992), etc.), a method of dehydrocondensing hydrosilanes in the presence of a specific polymerization metal catalyst (Japanese Patent Laid-Open No. Hei 4-). No. 334551, etc.), and disilee crosslinked with biphenyl or the like The method according to anionic polymerization (Macromolecules, 23,4494 (1990), etc.), methods and the like by the ring-opening polymerization of cyclic silanes.

  As the polysilazane compound, the formula (f)

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

In formula (f), n represents an arbitrary natural number.
Rm, Rp, and Rt each independently represent a non-hydrolyzable group such as a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or an alkylsilyl group.

Examples of the alkyl group, alkenyl group, and aryl group are the same as those exemplified for Rx and the like.
Examples of the cycloalkyl group are the same as those exemplified for Rq and the like.

  Examples of the alkylsilyl group include trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, tri-t-butylsilyl group, methyldiethylsilyl group, dimethylsilyl group, diethylsilyl group, methylsilyl group, and ethylsilyl group.

  Among these, as Rm, Rp, and Rt, a hydrogen atom, a C1-C6 alkyl group, or a phenyl group is preferable, and a hydrogen atom is especially preferable.

Examples of the polysilazane compound having a repeating unit represented by the formula (h) include inorganic polysilazanes in which Rm, Rp, and Rt are all hydrogen atoms, and organic polysilazanes in which at least one of Rm, Rp, and Rt is not a hydrogen atom. It may be.
As inorganic polysilazane, the following formula

Perhydropolysilazane having a linear structure having a repeating unit represented by formula (1), a molecular weight of 690 to 2000, and 3 to 10 SiH ₃ groups in one molecule (Japanese Patent Publication No. 63-16325) , Formula (A)

[Wherein, b and c represent an arbitrary natural number, and Y ¹ represents a hydrogen atom or a formula (B)

(Wherein, d represents an arbitrary natural number, * represents a bonding position, and Y ² represents a hydrogen atom or a group represented by (B) above). A perhydropolysilazane having a linear structure and a branched structure, having a repeating unit represented by formula (C):

And perhydropolysilazane having a linear structure, a branched structure and a cyclic structure in the molecule.

As organic polysilazane,
(I) — (Rm′SiHNH) — (Rm ′ represents the same alkyl group, cycloalkyl group, alkenyl group, aryl group or alkylsilyl group as Rm. The same applies to the following Rm ′). As a unit, mainly having a cyclic structure with a degree of polymerization of 3-5,
(Ii) — (Rm′SiHNRt ′) — (Rt ′ represents the same alkyl group, cycloalkyl group, alkenyl group, aryl group or alkylsilyl group as Rt), and the degree of polymerization is mainly 3 Having a ring structure of ~ 5,
(Iii) — (Rm′Rp′SiNH) — (Rp ′ represents an alkyl group, cycloalkyl group, alkenyl group, aryl group alkylsilyl group similar to Rp) as a repeating unit, and the degree of polymerization is mainly 3 Having a ring structure of ~ 5,
(Iv) a polyorgano (hydro) silazane having a structure represented by the following formula in the molecule;

(V) The following formula

[Rm ′ and Rp ′ represent the same meaning as described above, e and f represent an arbitrary natural number, and Y ³ represents a hydrogen atom or the following formula (D)

(Wherein g represents an arbitrary natural number, * represents a bonding position, and Y ⁴ represents a hydrogen atom or a group represented by (D) above). ]
And polysilazane having a repeating structure represented by

  The organic polysilazane can be produced by a conventionally known method. For example, the following formula

(In the formula, m represents 2 or 3, X represents a halogen atom, and R ¹ represents any of the substituents of Rm, Rp, Rt, Rm ′, Rp ′, and Rt ′ described above.) It can obtain by making ammonia or a primary amine react with the reaction product of the halogenosilane compound and the secondary amine which have an unsubstituted or substituted group.
The secondary amine, ammonia, and primary amine to be used may be appropriately selected according to the structure of the target polysilazane compound.

In the present invention, a modified polysilazane compound can also be used as the polysilazane compound. Examples of the modified polysilazane include, for example, a polymetallosilazane containing a metal atom (the metal atom may be crosslinked), and repeating units of [(SiH ₂ ) _j (NH) _h )] and [(SiH ₂ ) _i O] (wherein, j, h, i are each independently 1, 2 or 3. polysiloxazane (JP 62-195024 discloses represented by)), boron compound polysilazane Polyborosilazane produced by reacting polysilazane (JP-A-2-84437), polymetallosilazane produced by reacting polysilazane and metal alkoxide (JP-A-63-81122, etc.), high inorganic silazane polymer And modified polysilazanes (JP-A-1-138108, etc.), copolymer silazanes obtained by introducing organic components into polysilazane (JP-A-2-175726, etc.), Low temperature ceramicized polysilazane (Japanese Patent Laid-Open No. 5-238827 etc.) in which a catalytic compound for promoting ceramification is added or added to lysilazane,
Silicon alkoxide-added polysilazane (Japanese Patent Laid-Open No. 5-238827), glycidol-added polysilazane (Japanese Patent Laid-Open No. 6-122852), acetylacetonato complex-added polysilazane (Japanese Patent Laid-Open No. 6-306329), metal carboxylate-added polysilazane ( JP-A-6-299118)
A polysilazane composition obtained by adding amines and / or acids to the polysilazane or a modified product thereof (Japanese Patent Laid-Open No. 9-31333), perhydropolysilazane with alcohol such as methanol or hexamethyldisilazane as a terminal N atom Examples thereof include modified polysilazanes obtained by addition (JP-A-5-345826, JP-A-4-63833) and the like.

Among these, as the polysilazane compound used in the present invention, inorganic polysilazane in which Rm, Rp, and Rt are all hydrogen atoms, and organic polysilazane in which at least one of Rm, Rp, and Rt is not a hydrogen atom are preferable and easily available. From the viewpoint of forming an injection layer having excellent gas barrier properties, inorganic polysilazane is more preferable.
In addition, the polysilazane type compound can also use the commercial item marketed as a glass coating material etc. as it is.

  Among these, in the film of the present invention, since the ion-implanted layer having excellent gas barrier properties and the like is obtained, the polymer layer seems to contain a silicon-based polymer compound, polyester or acrylic resin. The layer containing a silicon-based polymer compound is more preferable.

  The polymer layer may contain other components in addition to the above-described polymer compound as long as the object of the present invention is not impaired. Examples of other components include curing agents, other polymers, anti-aging agents, light stabilizers, and flame retardants.

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

  The method for forming the polymer layer is not particularly limited, and for example, a layer forming solution containing at least one polymer compound, optionally other components, and a solvent is applied on the primer layer, The method of drying and forming the obtained coating film moderately is mentioned.

  As the coating apparatus, known apparatuses such as a spin coater, a knife coater, and a gravure coater can be used.

  In order to dry the obtained coating film and improve the gas barrier property of the film, it is preferable to heat the coating film. Heating is performed at 80 to 150 ° C. for several tens of seconds to several tens of minutes.

The thickness of the formed polymer layer is not particularly limited, but is usually 20 nm to 1000 nm, preferably 30 to 500 nm, and more preferably 40 to 200 nm.
In the present invention, a film having sufficient gas barrier performance can be obtained even if the thickness of the polymer layer is nano-order.

(Ion implantation)
The film of the present invention has a layer (gas barrier layer) obtained by implanting ions into a polymer layer.
What is necessary is just to determine suitably the injection amount of the ion inject | poured into a polymer layer according to the intended purpose (necessary gas barrier property, transparency, etc.) of the film to form.

As ions to be implanted, ions of rare gases such as argon, helium, neon, krypton, and xenon; ions such as fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, and sulfur;
Ions of alkane gases such as methane, ethane, propane, butane, pentane and hexane; ions of alkene gases such as ethylene, propylene, butene and pentene; ions of alkadiene gases such as pentadiene and butadiene; acetylene, Ions of alkyne gases such as methylacetylene; ions of aromatic hydrocarbon gases such as benzene, toluene, xylene, indene, naphthalene and phenanthrene; ions of cycloalkane gases such as cyclopropane and cyclohexane; cyclopentene, Ions of cycloalkene gases such as cyclohexene;
Ions of conductive metals such as gold, silver, copper, platinum, nickel, palladium, chromium, titanium, molybdenum, niobium, tantalum, tungsten, aluminum;
Silane (SiH ₄ ) or an ion of an organosilicon compound;

Examples of the organosilicon compound include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, and tetra t-butoxysilane;
An alkylalkoxysilane having an unsubstituted or substituted group such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane;
Arylalkoxysilanes such as diphenyldimethoxysilane and phenyltriethoxysilane;
Disiloxanes such as hexamethyldisiloxane (HMDSO);
Aminosilanes such as bis (dimethylamino) dimethylsilane, bis (dimethylamino) methylvinylsilane, bis (ethylamino) dimethylsilane, diethylaminotrimethylsilane, dimethylaminodimethylsilane, tetrakisdimethylaminosilane, tris (dimethylamino) silane;
Silazanes such as hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, nonamethyltrisilazane, octamethylcyclotetrasilazane, tetramethyldisilazane;
Cyanate silanes such as tetraisocyanate silane;
Halogenosilanes such as triethoxyfluorosilane;
Alkenylsilanes such as diallyldimethylsilane and allyltrimethylsilane;
Alkyl silanes having no substituents or substituents such as di-t-butylsilane, 1,3-disilabutane, bis (trimethylsilyl) methane, tetramethylsilane, tris (trimethylsilyl) methane, tris (trimethylsilyl) silane, benzyltrimethylsilane;
Silylalkynes such as bis (trimethylsilyl) acetylene, trimethylsilylacetylene, 1- (trimethylsilyl) -1-propyne;
Silylalkenes such as 1,4-bistrimethylsilyl-1,3-butadiyne, cyclopentadienyltrimethylsilane;
Arylalkylsilanes such as phenyldimethylsilane and phenyltrimethylsilane;
Alkynylalkylsilanes such as propargyltrimethylsilane;
Alkenylalkylsilanes such as vinyltrimethylsilane;
Disilanes such as hexamethyldisilane;
Siloxanes such as octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, hexamethylcyclotetrasiloxane;
N, O-bis (trimethylsilyl) acetamide;
Bis (trimethylsilyl) carbodiimide;
Etc.
These ions may be used alone or in combination of two or more.

  Among them, at least selected from the group consisting of hydrogen, nitrogen, oxygen, argon, helium, neon, xenon, and krypton, because a gas barrier layer that can be more easily injected and has a particularly excellent gas barrier property can be obtained. One kind of ion is preferred.

  A method for implanting ions is not particularly limited, and examples include a method of irradiating ions accelerated by an electric field (ion beam), a method of implanting ions in plasma, and the like. Among them, in the present invention, the latter method of implanting plasma ions is preferable because a gas barrier film can be easily obtained.

  In the plasma ion implantation, for example, plasma is generated in an atmosphere containing a plasma generation gas such as a rare gas, and a negative high voltage pulse is applied to the polymer layer, whereby ions (positive ions) in the plasma are It can carry out by injecting into the surface part of the layer containing a silicon compound.

  The thickness of the portion into which ions are implanted can be controlled by implantation conditions such as the type of ion, applied voltage, treatment time, etc., and can be determined according to the thickness of the layer containing the silicon compound, the purpose of use of the film, etc. Usually, it is 10 to 1000 nm.

  The ion implantation can be confirmed by performing elemental analysis measurement in the vicinity of 10 nm from the surface using X-ray photoelectron spectroscopy (XPS).

  The film of the present invention has a gas barrier layer on at least one surface side of the base film via a primer layer, but may further include other layers. Further, the other layer may be a single layer or two or more layers of the same type or different types. Examples of other layers include an inorganic thin film layer, a conductor layer, and a shock absorbing layer.

  The inorganic thin film layer is a layer composed of one or more inorganic compounds. Inorganic compounds that can be generally formed in a vacuum and have a gas barrier property, such as inorganic oxides, inorganic nitrides, inorganic carbides, inorganic sulfides, inorganic oxynitrides and inorganic oxide carbides that are composites thereof Inorganic nitride carbide, inorganic oxynitride carbide, and the like.

  The thickness of the inorganic thin film layer is usually in the range of 10 nm to 1000 nm, preferably 20 to 500 nm, more preferably 20 to 100 nm.

  Examples of the material constituting the conductor layer include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Specifically, antimony-doped tin oxide (ATO); fluorine-doped tin oxide (FTO); half of tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), etc. Conductive metal oxides; metals such as gold, silver, chromium and nickel; mixtures of these metals and conductive metal oxides; inorganic conductive materials such as copper iodide and copper sulfide; organics such as polyaniline, polythiophene and polypyrrole Conductive materials; and the like.

  There is no restriction | limiting in particular as a formation method of a conductor layer. For example, vapor deposition, sputtering, ion plating, thermal CVD, plasma CVD, and the like can be given.

  What is necessary is just to select the thickness of a conductor layer suitably according to the use. The thickness is usually 10 nm to 50 μm, preferably 20 nm to 20 μm.

The material for forming the shock absorbing layer is not particularly limited, and examples thereof include acrylic resins, urethane resins, silicone resins, olefin resins, and rubber materials.
Moreover, what is marketed as an adhesive, a coating agent, a sealing agent etc. can also be used, and adhesives, such as an acrylic adhesive, a silicone adhesive, and a rubber adhesive, are especially preferable.

There is no restriction | limiting in particular as a formation method of an impact-absorbing layer, For example, the material (adhesive etc.) which forms the said impact-absorbing layer similarly to the formation method of the said layer containing a silicon compound, and a solvent etc. depending on necessity Examples include a method in which a shock absorbing layer forming solution containing other components is applied onto a layer to be laminated, the obtained coating film is dried, and heated, if necessary.
Alternatively, a shock absorbing layer may be separately formed on the release substrate, and the obtained film may be transferred and stacked on the layer to be stacked.
The thickness of the shock absorbing layer is usually 1 to 100 μm, preferably 5 to 50 μm.

When the film of the present invention is a laminate including other layers, the arrangement position of the other layers is not particularly limited as long as the primer layer and the gas barrier layer are adjacent to each other.
The gas barrier layer may be formed on one side of the base film via a primer layer, or may be formed on both sides of the base film via a primer layer.

  The film of the present invention is excellent in interlayer adhesion. It can be confirmed that the film of the present invention has excellent interlayer adhesion, for example, by performing a test in which an adhesive tape according to JIS-K5600-5-6 is applied and peeled off, and the evaluation is good. .

  The film of the present invention is excellent in surface smoothness. The excellent surface smoothness of the film of the present invention can be confirmed, for example, by measuring the surface roughness Ra value (nm) in the measurement region 1 × 1 μm using an atomic force microscope (AFM). . The Ra value at 1 × 1 μm is preferably 0.45 nm or less.

The film of the present invention is excellent in gas barrier properties. It can be confirmed that the film of the present invention has gas barrier properties because the water vapor permeability of the film of the present invention is small. For example, the water vapor transmission rate is preferably 0.5 g / m ² / day or less in an atmosphere of 40 ° C. and a relative humidity of 90%. The transmittance of the film such as water vapor can be measured using a known gas permeability measuring device.

  The film of the present invention is excellent in transparency. It can be confirmed that the film of the present invention has excellent transparency because the visible light transmittance of the film of the present invention is high. The visible light transmittance is a transmittance at a wavelength of 550 nm, and is preferably 74% or more. The visible light transmittance of the film can be measured using a known visible light transmittance measuring device.

(Method for producing gas barrier film)
In the film of the present invention, a primer layer is formed on the surface of the base film on which the gas barrier layer is formed, a polymer layer is laminated on the primer layer, and then ions are applied to the surface portion of the polymer layer. It can be manufactured by injection.

  In the production of the film of the present invention, the step of injecting ions is a step of injecting ions into the polymer layer while conveying a long laminate having the polymer layer on the surface portion in a certain direction. Is preferred. According to this manufacturing method, for example, a long laminate can be unwound from an unwinding roll, and the ions can be injected while being conveyed in a certain direction, and taken up by the winding roll. The film obtained can be continuously produced.

  The thickness of the obtained laminate is preferably 1 μm to 500 μm, and more preferably 5 μm to 300 μm, from the viewpoint of unwinding, winding and conveying operability.

  The method for implanting ions into the polymer layer is not particularly limited. Among these, as described above, the plasma ion implantation method is particularly preferable.

  As the plasma ion implantation method, (A) a method in which ions existing in plasma generated using an external electric field are implanted into the surface portion of the polymer layer, or (B) the layer without using an external electric field. A method is preferred in which ions existing in plasma generated only by an electric field generated by a negative high voltage pulse applied to are implanted into the surface portion of the polymer layer.

  In the method (A), the pressure during ion implantation (pressure during plasma ion implantation) is preferably 0.01 to 1 Pa. When the pressure during plasma ion implantation is in such a range, ions can be implanted easily and efficiently uniformly, and a gas barrier layer having both bending resistance and gas barrier properties can be efficiently formed. .

  In the method (B), it is not necessary to increase the degree of reduced pressure, the processing operation is simple, and the processing time can be greatly shortened. Further, the entire layer can be processed uniformly, and ions in the plasma can be continuously injected into the surface portion of the layer with high energy when a negative high voltage pulse is applied. Furthermore, without applying special other means such as radio frequency (hereinafter abbreviated as “RF”) or a high-frequency power source such as a microwave, just applying a negative high voltage pulse to the layer, A high-quality ion-implanted layer can be uniformly formed on the surface of the layer.

  In both methods (A) and (B), the pulse width when applying a negative high voltage pulse, that is, when implanting ions, is preferably 1 to 15 μsec. When the pulse width is in such a range, ions can be implanted more easily and efficiently and uniformly.

  The applied voltage when generating plasma is preferably -1 kV to -50 kV, more preferably -1 kV to -30 kV, and particularly preferably -5 kV to -20 kV. When ion implantation is performed with an applied voltage greater than −1 kV, the ion implantation amount (dose amount) becomes insufficient, and desired performance cannot be obtained. On the other hand, if ion implantation is performed at a value smaller than −50 kV, the film is charged at the time of ion implantation, and defects such as coloring of the film are not preferable.

  Examples of ion species for plasma ion implantation include the same ions as those exemplified as the ions to be implanted.

When ions in plasma are implanted into the surface portion of the layer, a plasma ion implantation apparatus is used.
Specifically, a plasma ion implantation apparatus superimposes high-frequency power on a feedthrough that applies a negative high-voltage pulse to a polymer layer (hereinafter, also referred to as “ion-implanted layer”). A device for uniformly enclosing the periphery of the ion-implanted layer with plasma and attracting, implanting, colliding and depositing ions in the plasma (Japanese Patent Laid-Open No. 2001-26887), (β) An antenna is provided in the chamber, and high-frequency power is provided. After the plasma reaches the periphery of the layer to be ion-implanted by applying plasma, positive and negative pulses are alternately applied to the layer to be ion-implanted, so that the electrons in the plasma are attracted and collided with the positive pulse. An apparatus for attracting and implanting ions in plasma by applying a negative pulse while heating a layer to be ion-implanted and controlling the temperature by controlling the pulse constant (Japanese Patent Laid-Open No. 2001-1560) 13), (γ) a plasma ion implantation apparatus for generating plasma using an external electric field such as a high-frequency power source such as a microwave, and applying high voltage pulses to attract and inject ions in the plasma, (δ And a plasma ion implantation apparatus that implants ions in plasma generated only by an electric field generated by applying a high voltage pulse without using an external electric field.

Among these, it is preferable to use the plasma ion implantation apparatus (γ) or (δ) because the processing operation is simple, the processing time can be greatly shortened, and it is suitable for continuous use.
Hereinafter, a method using the plasma ion implantation apparatuses (γ) and (δ) will be described in detail with reference to the drawings.

FIG. 1 is a diagram showing an outline of a continuous plasma ion implantation apparatus including the plasma ion implantation apparatus (γ).
In FIG. 1A, 1a is a long laminate (hereinafter referred to as “film”) obtained by sequentially forming a primer layer and a polymer layer on a base film, 11a is a chamber, and 20a is An oil diffusion pump, 3a is an unwinding roll for feeding out the film 1a before being ion-implanted, 5a is a winding roll for winding the ion-implanted film 1b in a roll shape, 2a is a high-voltage applied rotation can, 6a is a film A delivery roll, 10a is a gas inlet, 7a is a high voltage pulse power source, and 4 is an electrode for plasma discharge (external electric field). FIG. 1B is a perspective view of the high-voltage applying rotation can 2a, and 15 is a high-voltage introduction terminal (feedthrough).

  In the continuous plasma ion implantation apparatus shown in FIG. 1, the film 1a is transported in the chamber 11a from the unwinding roll 3a in the direction of the arrow X in FIG. It is wound up on a roll 5a. There are no particular restrictions on the method for winding the film 1b, the method for transporting the film 1a, etc. In this embodiment, the film 1a is transported by rotating the high-voltage applying rotation can 2a at a constant speed. ing. The rotation of the high voltage application rotation can 2a is performed by rotating the central shaft 13 of the high voltage introduction terminal 15 by a motor.

  The high voltage introduction terminal 15 and the plurality of delivery rolls 6a with which the film 1a comes into contact are made of an insulator, for example, formed by coating the surface of alumina with a resin such as polytetrafluoroethylene. Moreover, the high voltage application rotation can 2a is made of a conductor, and can be formed of stainless steel, for example.

  The conveyance speed of the film 1a can be set as appropriate. The film 1a is conveyed from the unwinding roll 3a and is ion-implanted into the surface portion (layer containing the silicon-based polymer compound) until the film 1a is wound on the winding roll 5a to form a desired ion-implanted layer. The speed is not particularly limited as long as the time is sufficient to be secured. The film winding speed (conveyance speed) is usually 0.1 to 3 m / min, preferably 0.2 to 2.5 m / min, although it depends on the applied voltage, the apparatus scale, and the like.

First, the chamber 11a is evacuated by an oil diffusion pump 20a connected to a rotary pump to reduce the pressure. The degree of reduced pressure is usually 1 × 10 ⁻² Pa or less, preferably 1 × 10 ⁻³ Pa or less.

  Next, a gas for ion implantation such as nitrogen is introduced into the chamber 11a from the gas inlet 10a, and the inside of the chamber 11a is set to a reduced pressure ion implantation gas atmosphere. The pressure at the time of ion implantation (the pressure of the plasma gas in the chamber 11a) is preferably 0.01 to 1 Pa. The ion implantation gas is also a plasma generation gas.

  Next, plasma is generated by the plasma discharge electrode 4 (external electric field). As a method for generating plasma, a known method using a high-frequency power source such as a microwave or RF may be used.

  On the other hand, a negative high voltage pulse 9a is applied by a high voltage pulse power source 7a connected to the high voltage application rotation can 2a via a high voltage introduction terminal 15. When a negative high-voltage pulse is applied to the high-voltage application rotation can 2a, ions in the plasma are induced and injected into the surface of the film around the high-voltage application rotation can 2a (in FIG. 1A, the arrow Y) A film 1b is obtained.

  Next, a method of performing ion implantation on the film surface using the continuous plasma ion implantation apparatus shown in FIG. 2 will be described.

  The apparatus shown in FIG. 2 includes the plasma ion implantation apparatus (δ). This plasma ion implantation apparatus generates plasma only by an electric field by a high voltage pulse applied without using an external electric field (that is, plasma discharge electrode 4 in FIG. 1).

  In the continuous plasma ion implantation apparatus shown in FIG. 2, the film 1c is conveyed in the direction of the arrow X in FIG. 2 from the unwinding roll 3b by rotating the high voltage application rotating can 2b as in the apparatus of FIG. Then, it is wound around the winding roll 5b.

  Ion implantation into the surface portion of the polymer layer of the film 1c by the continuous plasma ion implantation apparatus shown in FIG. 2 is performed as follows.

  First, as in the plasma ion implantation apparatus shown in FIG. 1, the film 1c is placed in the chamber 11b, and the inside of the chamber 11b is evacuated by an oil diffusion pump 20b connected to a rotary pump to reduce the pressure. Thereto, an ion implantation gas such as nitrogen is introduced into the chamber 11b from the gas introduction port 10b, and the inside of the chamber 11b is made a reduced pressure ion implantation gas atmosphere.

  The pressure at the time of ion implantation (the pressure of the plasma gas in the chamber 11b) is 10 Pa or less, preferably 0.01 to 5 Pa, more preferably 0.01 to 1 Pa.

  Next, the high voltage pulse power supply 7b connected to the high voltage application rotation can 2b through the high voltage introduction terminal (not shown) is conveyed while the film 1c is conveyed in the direction of X in FIG. Apply 9b.

  When a negative high voltage is applied to the high-voltage application rotation can 2b, plasma is generated along the film 1c around the high-voltage application rotation can 2b, and ions in the plasma are induced, and the high-voltage application rotation can 2b is induced. It is injected into the surface of the film 1c around 2b (arrow Y in FIG. 2). Ions are implanted into the surface portion of the polymer layer of the film 1c to obtain the film 1d.

  In the plasma ion implantation apparatus shown in FIG. 2, since the plasma generating means for generating plasma is also used by the high voltage pulse power source, no special other means such as a high frequency power source such as RF or microwave is required. Just by applying a negative high voltage pulse, plasma is generated, ions in the plasma are continuously injected into the surface of the polymer layer, and the film of the present invention in which the gas barrier layer is formed on the surface is mass-produced. be able to.

  The film of the present invention obtained as described above is excellent in all of interlayer adhesion, surface smoothness, gas barrier property and transparency, so that it is a packaging material for food, pharmaceuticals, etc .; liquid crystal display, organic EL display, inorganic EL display It can use suitably for display members, such as; electronic paper; back sheet for solar cells;

2) Electronic device member The electronic device member of the present invention comprises the gas barrier film of the present invention.
Since the electronic device member of the present invention is composed of the gas barrier film of the present invention having excellent gas barrier properties, interlayer adhesion, surface smoothness and transparency, it is flexible and can be reduced in weight. It is suitable as a member such as a display member such as a display or an EL display; a solar battery back sheet used for a solar battery or 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.

  The plasma ion implantation apparatus used, ion implantation confirmation, visible light transmittance measuring device and measurement conditions, surface smoothness evaluation method, gas barrier property evaluation (water vapor permeability measuring device and measurement conditions), and adhesion test are as follows: Street.

(Plasma ion implantation equipment)
RF power source: JEOL Ltd., model number “RF” 56000
High-voltage pulse power supply: “PV-3-HSHV-0835” manufactured by Kurita Manufacturing Co., Ltd.

(Confirmation of ion implantation)
The ion implantation was confirmed by measuring the gas barrier layer obtained by ion implantation using XPS (manufactured by ULVAC-PHI, Quantum 2000).

(Measurement of visible light transmittance)
The transmittance of the obtained gas barrier film at a wavelength of 550 nm was measured using an ultraviolet-visible near-infrared spectral transmittance meter (manufactured by Shimadzu Corporation, UV3600).

(Evaluation of surface smoothness)
The surface smoothness was evaluated by measuring Ra (nm) on the surface of the obtained gas barrier film using an atomic force microscope (AFM: SPA300 HV manufactured by SII Nanotechnology).

(Evaluation of gas barrier properties)
Using a water vapor transmission rate measuring device (L80-5000, manufactured by Lyssy), the water vapor transmission rate of the obtained gas barrier film under the conditions of RH 90% and 40 ° C. was measured and evaluated.

(Adhesion test)
The obtained gas barrier film was evaluated by a cross-cut test using a cellophane tape (JIS-K5600-5-6) (0: good to 5: bad, 6 stages).

Example 1
A coating solution containing a polysilicate compound as a primer layer on a base film made of a polyethylene terephthalate film (trade name “PET 38 T-100” manufactured by Mitsubishi Plastics Co., Ltd.) having a thickness of 38 μm (trade name “manufactured by Colcoat Co., Ltd. Colcoat N-103X ") was applied by spin coating and dried to form a silicate thin film (primer layer) having a thickness of 50 nm. Thereafter, a silicone resin (trade name “KS835” manufactured by Shin-Etsu Chemical Co., Ltd.) is applied onto the silicate thin film and dried to form a polyorganosiloxane layer (polymer layer) having a thickness of 100 nm. Argon ions were injected into the polymer layer by an injection method to obtain a film 1 of Example 1.

Plasma ion implantation was performed under the following conditions.
Plasma generation gas: Ar
Duty ratio: 0.5%
Repeat frequency: 1000Hz
Applied voltage: -10 kV
Chamber internal pressure: 0.2 Pa
Pulse width: 5μsec
Processing time: 5 minutes

(Example 2)
A film 2 of Example 2 was obtained in the same manner as in Example 1 except that the applied voltage was changed to -5 kV in Example 1.

(Example 3)
A film 3 of Example 3 was obtained in the same manner as in Example 1 except that the applied voltage was changed to -15 kV in Example 1.

Example 4
In Example 1, a film 4 of Example 4 was obtained in the same manner as in Example 1 except that the plasma generating gas was changed from argon to nitrogen.

(Example 5)
A film 5 of Example 5 was obtained in the same manner as in Example 1 except that the plasma generation gas was changed from argon to helium in Example 1.

(Example 6)
In Example 1, except that the polysilicate compound was changed to polysilazane (manufactured by AZ Electronics Co., Ltd., trade name: Aquamica NP110) to form a primer layer, the film 6 of Example 6 was prepared in the same manner as in Example 1. Obtained.

(Example 7)
The film of Example 7 was obtained in the same manner as in Example 1 except that the primer layer was formed by changing the polysilicate compound to polycarbosilane (trade name: Nypsy TypeS, manufactured by Nippon Carbon Co., Ltd.). 7 was obtained.

(Example 8)
A film 8 of Example 8 was obtained in the same manner as in Example 1 except that the primer layer was formed by changing the polysilicate compound to polysilane (manufactured by Osaka Gas Chemical Co., Ltd., trade name: Gusol SI10). Got.

Example 9
In Example 1, the polysilicate compound was changed to a polymer silane coupling agent (manufactured by GE Toshiba Silicone, trade name: YP9341), and a primer layer having a thickness of 500 nm was formed. Thus, a gas barrier film 9 of Example 9 was obtained.

(Comparative Example 1)
The untreated polyethylene terephthalate film used in Example 1 was used as the film 10 of Comparative Example 1 as it was.

(Comparative Example 2)
A film 11 of Comparative Example 2 was obtained in the same manner as in Example 1 except that ion implantation was not performed on the polyorganosiloxane layer in Example 1.

(Comparative Example 3)
In Example 1, the film 12 of the comparative example 3 was obtained like Example 1 except not providing a primer layer.

(Evaluation results)
For each of the films 1 to 12 obtained above, confirmation of ion implantation, measurement of visible light transmittance, evaluation of surface smoothness, evaluation of gas barrier properties, and adhesion test were performed.
The measurement results and evaluation results are shown in Table 1 below. Further, in the adhesion test, the electron micrograph after the cross-cut test (JIS-K5600-5-6) using cellophane tape was performed for the gas barrier films obtained in Example 1 and Comparative Example 3 in FIG. Example 1) and FIG. 4 (Comparative Example 3).

  From Table 1, the films 1 to 9 of Examples 1 to 9 and the film 12 of Comparative Example 3 have a smaller Ra value than the films 10 and 11 of Comparative Examples 1 and 2, and are excellent in surface smoothness. I understand that. It can be seen that the films 1 to 9 of Examples 1 to 9 and the film 12 of Comparative Example 3 have a smaller water vapor permeability than the films 10 and 11 of Comparative Examples 1 and 2, and are excellent in gas barrier properties. The films 1 to 9 of Examples 1 to 9 were excellent in interlayer adhesion as compared with the film 12 of Comparative Example 3. This can be seen from FIGS. Moreover, it turns out that the films 1-9 of Examples 1-9 have high visible light transmittance, and are excellent also in transparency.

1a, 1c ... Laminate (film)
1b, 1d ... Laminate (film)
2a, 2b ... rotating can 3a, 3b ... unwinding roll 4 ... plasma discharge electrodes 5a, 5b ... winding rolls 6a, 6b ... sending rolls 7a, 7b ... pulse Power supply 9a, 9b ... High voltage pulse 10a, 10b ... Gas introduction port 11a, 11b ... Chamber 13 ... Center axis 15 ... High voltage introduction terminal 20a, 20b ... Oil diffusion pump

Claims (7)

  A gas barrier film comprising a layer obtained by implanting ions into a polymer layer via a primer layer on at least one surface side of a base film.   The gas barrier film according to claim 1, wherein the polymer layer is a layer containing a silicon-based polymer compound.   The gas barrier film according to claim 1 or 2, wherein the primer layer is made of a silicon-containing compound.   4. The primer layer according to claim 1, wherein the primer layer is formed of at least one silicon-containing compound selected from the group consisting of polysilicate, polysilazane, polycarbosilane, polysilane, and a silane coupling agent. The gas barrier film according to any one of the above.   The gas barrier film according to any one of claims 1 to 4, wherein the polymer layer has a layer obtained by implanting ions by plasma ion implantation. The gas barrier film according to any one of claims 1 to 5, which has a water vapor permeability of less than 0.5 g / m ² / day in an atmosphere of 40 ° C and a relative humidity of 90%.   The member for electronic devices which consists of a gas-barrier film in any one of Claims 1-6.

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