JP2016172244A - Coating liquid supply device, coating liquid supply method, manufacturing method of lamination body, manufacturing method of gas barrier film, lamination body, and gas barrier film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To feed a high quality coating liquid to a coating device even if the coating liquid contains a chemical compound which may increase its molecular weight when the coating liquid is stored and/or fed.SOLUTION: A coating liquid supply device supplies a coating liquid to a coating device 5 and includes: a coating liquid tank 2 which stores the coating liquid; a feed pump 3 which transfers the coating liquid from the coating liquid tank 2 to the coating device 5; a specific filter 4 which filters the coating liquid fed from the coating liquid tank 2; and a feed pipe which connects the coating liquid tank 2, the feed pump 3, the filter 4, and the coating device 5 and feeds the coating liquid from the coating liquid tank 2 to the coating device 5. The above object is achieved by the coating liquid supply device, a coating liquid supply method in which the coating liquid is fed to the coating device 5 by using the coating liquid supply device, a manufacturing method of a lamination body or gas barrier film which uses the coating liquid supplied by using the coating liquid supply method, and the lamination body or gas barrier film obtained by the manufacturing method.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a coating liquid supply apparatus capable of feeding a high-quality coating liquid to a coating apparatus, even if the coating liquid contains a compound that can be polymerized during storage and / or liquid feeding, and this apparatus. A coating liquid supply method for feeding the coating liquid to a coating apparatus, a laminate or a gas barrier film manufacturing method using the coating liquid supplied using this method, and the manufacturing method. The present invention relates to a laminate or a gas barrier film.

In recent years, reactive compounds such as polyorganosiloxane compounds and polysilazane compounds have been used as gas barrier layer forming materials and coating agent components.
For example, Patent Document 1 describes a molded body having a layer in which ions are implanted into a layer containing a polysilazane compound obtained by applying and drying a coating liquid containing a polysilazane compound on a substrate. ing. This document also describes that a layer obtained by ion implantation functions as a gas barrier layer.
Patent Document 2 describes a coating solution containing alkoxysilane and perhydropolysilazane. This document also describes that by using this coating solution, a surface layer excellent in scratch resistance, antistatic property, anti-condensation property and the like can be formed on the surface of a plastic molded article or the like.

  In relation to the present invention, Patent Document 3 describes a production apparatus for producing a laminate by applying a solution containing a polysilazane composition to a substrate.

JP 2012-117150 A JP 2006-219538 A JP 2011-78941 A

As described above, by using a coating liquid containing a reactive compound such as a polyorganosiloxane compound or a polysilazane compound, a laminate having a functional thin film such as a gas barrier layer or a coating film can be efficiently produced. Can do.
However, the functional thin film formed by this method may not exhibit desired performance even if there is no problem in appearance depending on manufacturing conditions.

As a result of the inventors examining this cause, the reactive compound contained in the coating liquid becomes high molecular weight during storage and / or feeding of the coating liquid, and is mixed into the functional thin film as a minute foreign matter. In addition, the inventors have found that a functional thin film with poor performance is formed.
The present invention has been made on the basis of the above knowledge, and even if the coating liquid contains a compound capable of increasing the molecular weight during storage and / or liquid feeding, a high-quality coating liquid is fed to the coating apparatus. Coating liquid supply device capable of liquid, coating liquid supply method for feeding the coating liquid to the coating device using this device, laminate or gas barrier using the coating liquid supplied using this method It aims at providing the manufacturing method of a film, and the laminated body or gas barrier film obtained by this manufacturing method.

  In order to solve the above-mentioned problems, the present inventors diligently studied a coating liquid supply device. As a result, the coating liquid tank for storing the coating liquid, the liquid feeding pump for transferring the coating liquid from the coating liquid tank to the coating apparatus, and the coating liquid fed from the coating liquid tank are filtered. A coating comprising: a specific filter; a coating liquid tank, a liquid feeding pump, a filter and a coating apparatus; and a liquid feeding pipe for feeding the coating liquid from the coating liquid tank to the coating apparatus. Even if the liquid supply apparatus is a coating liquid containing a compound that can be polymerized during storage and / or liquid feeding, it has been found that a high-quality coating liquid can be fed to the coating apparatus. It came to be completed.

Thus, according to the present invention, the following (1) coating liquid supply device, (2) to (4) coating liquid supply method, (5) laminate production method, and (6) gas barrier film production. A method, a laminate of (7), and a gas barrier film of (8) are provided.
(1) A coating liquid supply apparatus for supplying a coating liquid to a coating apparatus,
A coating liquid tank for storing the coating liquid;
A liquid feed pump for transferring the coating liquid from the coating liquid tank to the coating apparatus;
A filter for filtering the coating liquid fed from the coating liquid tank;
A liquid feed pipe for connecting the coating liquid tank, a liquid feeding pump, a filter, and a coating apparatus, and feeding the coating liquid from the coating liquid tank to the coating apparatus;
With
The coating liquid supply apparatus, wherein the filter is made of a fluororesin and has a pore diameter of 0.50 μm or less.
(2) A coating liquid supply method for supplying a coating liquid containing a compound capable of high molecular weight during storage and / or liquid feeding and an organic solvent to a coating apparatus, the coating according to (1) A coating liquid supply method comprising: supplying a coating liquid in a coating liquid tank to a coating apparatus using a liquid supply apparatus.
(3) The compound that can be polymerized during the storage and / or liquid feeding is a compound that can react with moisture in the air during the storage and / or liquid feeding and can be polymerized. Coating liquid supply method.
(4) The coating liquid supply method according to (2) or (3), wherein the compound capable of increasing the molecular weight during storage and / or liquid feeding is a silicon-containing polymer.
(5) A coating film by coating a coating solution containing a compound capable of increasing the molecular weight during storage and / or liquid feeding and an organic solvent on the substrate or other layers formed on the substrate. A layer containing a compound capable of increasing the molecular weight during the storage and / or liquid feeding is formed by drying the coating film obtained in the step (A-1) and the step (A-1). Step (A-2),
A method for producing a laminate having
The coating liquid to be applied in the step (A-1) is supplied to the coating apparatus by the coating liquid supply method according to any one of (2) to (4). A manufacturing method of a layered product.
(6) A step of forming a coating film by applying a coating solution containing a silicon-containing polymer and an organic solvent on the base film or other layers formed on the base film (B-1 ),
A step (B-2) of forming a layer containing the silicon-containing polymer by drying the coating film obtained in the step (B-1); and
A step of modifying the layer containing the silicon-containing polymer obtained in the step (B-2) to form a gas barrier layer (B-3),
A method for producing a gas barrier film comprising:
The method for producing a gas barrier film, wherein the coating liquid to be applied in the step (B-1) is supplied to the coating apparatus by the coating liquid supply method described in (4).
(7) A laminate obtained by the method described in (5) above.
(8) A gas barrier film obtained by the method according to (6).

  According to the present invention, even a coating solution containing a compound that can be increased in molecular weight during storage and / or liquid feeding (hereinafter sometimes referred to as “compound (A)”) has good quality in the coating apparatus. Coating liquid supply apparatus capable of feeding the coating liquid of the present invention, a coating liquid supply method for feeding the coating liquid to the coating apparatus using this apparatus, and a coating liquid supplied using this method The manufacturing method of the laminated body or gas barrier film using this, and the laminated body or gas barrier film obtained by this manufacturing method are provided.

It is a schematic diagram showing the coating liquid supply apparatus used in the Example.

  Hereinafter, the present invention is divided into 1) a coating liquid supply device, 2) a coating liquid supply method, 3) a laminate manufacturing method and a laminate, and 4) a gas barrier film manufacturing method and a gas barrier film. This will be described in detail.

1) Coating liquid supply apparatus The coating liquid supply apparatus of this invention supplies a coating liquid to a coating apparatus, Comprising: The coating liquid tank which stores the said coating liquid, The said coating liquid A liquid feed pump for transferring the coating liquid from the tank to the coating apparatus, a filter for filtering the coating liquid sent from the coating liquid tank, and the coating liquid tank, the liquid feeding pump, the filter and the coating A liquid supply pipe for connecting the apparatus and supplying the coating liquid from the coating liquid tank to the coating apparatus, wherein the filter is made of fluororesin and has a pore diameter of 0.50 μm or less. It is characterized by.

  The coating liquid tank which comprises the coating liquid supply apparatus of this invention stores a coating liquid. In the coating liquid supply apparatus of the present invention, the capacity, material, etc. of the coating liquid tank are not particularly limited, and known ones can be used as appropriate. The material of the coating liquid tank is preferably a material that is not affected by the organic solvent contained in the coating liquid.

  The coating liquid stored in the coating liquid tank is not particularly limited. However, a coating liquid containing the compound (A) and an organic solvent is preferable because the characteristics of the coating liquid supply apparatus of the present invention can be fully utilized. By using the coating liquid supply apparatus of the present invention, it is possible to feed such a coating liquid that easily generates minute foreign matters to the coating apparatus in a high quality state.

  Examples of the compound (A) include compounds that can react with moisture in the air to increase the molecular weight. Specific examples include silicon-containing polymers such as polysilazane compounds and polyorganosiloxane compounds.

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

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

  In said formula (1), n represents arbitrary natural numbers. Rx, Ry, and Rz each independently represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted alkenyl group, unsubstituted or substituted Represents a non-hydrolyzable group such as an aryl group having a group or an alkylsilyl group

  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, C1-C10 alkyl groups, such as n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, are mentioned.

  Examples of the unsubstituted or substituted cycloalkyl group include cycloalkyl groups having 3 to 10 carbon atoms such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.

  Examples of the alkenyl group of an unsubstituted or substituted alkenyl group include, for example, a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, etc. 10 alkenyl groups are mentioned.

  Examples of the substituent for the alkyl group, cycloalkyl group and alkenyl group include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydroxyl group; thiol group; epoxy group; glycidoxy group; (meth) acryloyloxy group An unsubstituted or substituted aryl group such as a phenyl group, 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.

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

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

In the present invention, a modified polysilazane compound can also be used as the polysilazane compound. Examples of the modified polysilazane include, for example, JP-A-62-195024, JP-A-2-84437, JP-A-63-81122, JP-A-1-138108, and JP-A-2-175726. JP-A-5-238827, JP-A-5-238827, JP-A-6-122852, JP-A-6-306329, JP-A-6-299118, JP-A-9-31333, Examples thereof include those described in Kaihei 5-345826 and JP-A-4-63833.
Among these, as the polysilazane compound, perhydropolysilazane in which Rx, Ry, and Rz are all hydrogen atoms is preferable from the viewpoint of easy availability and the ability to form an ion-implanted layer having excellent gas barrier properties.
Moreover, as a polysilazane compound, a commercially available product as a glass coating material or the like can be used as it is.
The polysilazane compounds can be used alone or in combination of two or more.

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 structure represented by the following formula (a) as the linear main chain structure, and the structure represented by the following formula (b) as the ladder main chain structure is a cage-like polysiloxane compound. Examples of these include structures represented by the following formula (c).

  In formulas (a) to (c), Rx, Ry, and Rz each independently represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted group. It represents a non-hydrolyzable group such as an alkenyl group having a group, an unsubstituted or substituted aryl group, or an alkylsilyl 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.

  Specific examples of Rx, Ry, Rz in the formulas (a) to (c) include the same as those shown as Rx in the formula (1).

  The number average molecular weight of the polyorganosiloxane compound is not particularly limited, but is preferably 100 to 50,000.

  In the present invention, the polyorganosiloxane-based compound is preferably a linear compound represented by the formula (b), and is easily available and can form a polyorganosiloxane compound layer having excellent gas barrier properties. Therefore, polymethylsilsesquioxane, which is a compound in which both Rx in the formula (b) are methyl groups, 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.

  In addition, as the polyorganosiloxane compound, those commercially available as a release agent, an adhesive, a sealant and the like can be used as they are.

  The coating liquid may contain other components. Examples of other components include a curing agent, an anti-aging agent, a light stabilizer, and a flame retardant. The content of these components can be appropriately determined according to the purpose.

The organic solvent contained in the coating solution is not particularly limited as long as it dissolves the compound (A) and other components.
Examples of the organic solvent include aromatic hydrocarbon solvents such as benzene and toluene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; n-pentane, n-hexane, n -Aliphatic hydrocarbon solvents such as heptane; Alicyclic hydrocarbon solvents such as cyclopentane and cyclohexane; and the like.
These solvents can be used alone or in combination of two or more.

  The liquid feed pump constituting the coating liquid supply apparatus of the present invention transfers the coating liquid from the coating liquid tank to the coating apparatus. In the coating liquid supply apparatus of the present invention, the type of the liquid feed pump and the like are not particularly limited, and known ones can be used as appropriate. Examples of the liquid feed pump include a tube pump, a Mono pump, a centrifugal pump, a mixed flow pump, an axial pump, a mixed flow pump, a gear pump, a piston pump, a plunger pump, a vane pump, a screw pump, and a diaphragm pump.

  The filter which comprises the coating-liquid supply apparatus of this invention filters the coating liquid sent from a coating-liquid tank. Since this filter removes minute foreign matters in the coating liquid, a high-quality coating liquid is fed to the coating apparatus.

  The filter is made of a fluororesin. By using a coating liquid supply device whose filter is made of a fluororesin, a thin film with few impurities can be formed. That is, when a polypropylene or nylon filter is used, the resin component constituting the filter is likely to elute into the coating liquid during the feeding of the coating liquid. For this reason, when a functional thin film is formed using the coating liquid, the elution component is mixed into the thin film as a minute foreign substance, and a functional thin film with poor performance is easily formed.

  As fluororesin, polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), Examples thereof include tetrafluoroethylene / ethylene copolymer (ETFE) and tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA). Among these, polytetrafluoroethylene is preferable.

The pore size of the filter is 0.50 μm or less, preferably 0.10 μm or more and 0.45 μm or less.
When the pore size of the filter exceeds 0.50 μm, the removal of minute foreign matters in the coating liquid is not sufficient. When a functional thin film is formed using a coating liquid containing such a foreign substance, a minute foreign substance is mixed in the thin film, and a functional thin film with poor performance is easily formed. In particular, as will be described later, when the coating liquid contains the compound (A), when the filter is not provided, or when the pore size of the filter exceeds 0.50 μm, the molecular weight is increased to a fine particle. The component which became becomes mixed in a thin film, and it becomes easy to form the functional thin film inferior in performance.
In addition, since the foreign material removed by this filter is a very minute thing, even if this mixes into a thin film, it does not become a problem on an external appearance normally. However, as shown in the examples, the presence of the foreign substance can be confirmed by observing the thin film with an electron microscope. Further, as described above, even if such foreign matter does not cause a problem in appearance, it tends to greatly affect the performance of the functional thin film.

The liquid feeding pipe constituting the coating liquid supply apparatus of the present invention connects the coating liquid tank, the liquid feeding pump, the filter and the coating apparatus, and feeds the coating liquid from the coating liquid tank to the coating apparatus. Is.
The material of the liquid feeding pipe is not particularly limited as long as it can feed the coating liquid from the coating liquid tank to the coating apparatus, and a known pipe can be appropriately used. The material of the liquid feeding pipe is preferably a material that is not affected by the organic solvent contained in the coating liquid.

In the coating liquid supply apparatus of the present invention, the arrangement of the liquid feed pump, the filter and the like is not particularly limited. For example, you may connect in order of a coating liquid tank, a liquid feeding pump, a filter, and a coating apparatus, and you may connect in order of a coating liquid tank, a filter, a liquid feeding pump, and a coating apparatus.
Since a higher quality coating liquid can be supplied to the coating apparatus, the connection order is preferably a coating liquid tank, a liquid feed pump, a filter, and a coating apparatus.

  The coating liquid supply apparatus of the present invention may include apparatuses other than the coating liquid tank, the liquid feeding pump, the filter, and the liquid feeding pipe. For example, an inert gas cylinder or vacuum pump is connected to the coating liquid tank, etc., and the coating liquid supply device is filled with inert gas using these to supply the coating liquid to the coating device more stably. can do. Examples of the inert gas filled in the inert gas cylinder include nitrogen, helium, neon, argon, krypton, xenon, carbon dioxide, and the like, and one or a mixture of two or more types can be used.

As described above, the coating liquid supply apparatus of the present invention includes a filter made of a fluororesin and having a pore diameter of 0.50 μm or less. For this reason, by using the coating liquid supply apparatus of this invention, the coating liquid which hardly contains a micro foreign material can be stably supplied to a coating apparatus.
By coating such a coating solution on an object to be coated, a functional thin film having the desired performance can be efficiently formed.

2) Coating liquid supply method The coating liquid supply method of the present invention applies a coating liquid containing a compound [compound (A)] that can be polymerized during storage and / or liquid feeding, and an organic solvent. The coating liquid supply method supplies the coating liquid in the coating liquid tank to the coating apparatus using the coating liquid supply apparatus of the present invention.

The coating liquid used for the method of the present invention contains the compound (A) and an organic solvent. Examples of the compound (A) and the organic solvent in the method of the present invention include the same as those described above as constituting the coating liquid to be fed in the invention of the coating liquid supply apparatus.
The supply speed of the coating liquid is not particularly limited, and can be appropriately determined according to the coating amount.

  According to the method of the present invention, the coating liquid from which minute foreign matters are removed can be supplied to the coating apparatus. Then, by applying this coating liquid onto an object to be coated, a coating film containing almost no minute foreign matter can be formed.

3) Method for producing laminate and laminate The method for producing a laminate of the present invention is a compound capable of increasing the molecular weight during storage and / or liquid feeding on the substrate or other layers formed on the substrate. [Compound (A)] and a step (A-1) of forming a coating film by applying a coating solution containing an organic solvent, and drying the coating film obtained in the step (A-1) Thus, the step (A-2) for forming a layer containing the compound (A) is provided, and the coating liquid applied in the step (A-1) is the coating liquid of the present invention. It is what was supplied to the coating device by the supply method.

  Step (A-1) is a step of forming a coating film by applying a coating solution containing the compound (A) and an organic solvent on the substrate or other layers formed on the substrate. The coating liquid is supplied to the coating apparatus by the coating liquid supply method of the present invention.

  The base material to be used is not particularly limited as long as it has sufficient strength as the base material of the laminate. For example, polyolefin film such as polyethylene film and polypropylene film; polyester film such as polyethylene terephthalate (PET) film; polylactic acid resin film; resin film having a metal deposited film on the surface; paper such as synthetic paper, fine paper, impregnated paper A metal foil such as an aluminum foil, a copper foil, and an iron foil; a sheet made of a porous material such as a nonwoven fabric; and the like.

  The thickness of the substrate is not particularly limited and may be determined according to the purpose of the laminate. The thickness of a base material is 0.5-500 micrometers normally, Preferably it is 1-100 micrometers.

  The coating solution may be applied directly on the substrate, or may be applied on other layers such as a primer layer formed on the substrate. Other layers such as a primer layer can be formed on the substrate using a known method.

  Coating methods for coating liquids include bar coating, spin coating, dipping, roll coating, gravure coating, knife coating, air knife coating, roll knife coating, die coating, screen printing, and spraying. Examples thereof include a coating method and a gravure offset method.

  The thickness of the coating film is not particularly limited and can be appropriately determined according to the purpose of the laminate. The thickness of the coating film is usually 20 nm to 10 μm, preferably 30 to 500 nm, more preferably 40 to 400 nm.

  The coating liquid used in the production method of the present invention is supplied to the coating apparatus by the coating liquid supply method of the present invention, and minute foreign matters are removed. Therefore, the coating film which hardly contains minute foreign matters can be formed by the step (A-1).

A process (A-2) is a process of forming the layer containing the said compound (A) by drying the coating film obtained at the process (A-1).
As a method for drying the coating film, conventionally known drying methods such as hot air drying, hot roll drying, and infrared irradiation can be employed. The heating temperature is usually in the range of 60 to 130 ° C. The heating time is usually several seconds to several tens of minutes.

According to the method for producing a laminate of the present invention, it is possible to obtain a laminate having a layer containing the compound (A) that hardly contains minute foreign matters. A layer containing the compound (A) that hardly contains minute foreign matters can be used as a hard coat layer or the like.
Examples of the laminate obtained by the method of the present invention include an optical disk and a mirror.

4) Method for producing gas barrier film and gas barrier film The method for producing a gas barrier film of the present invention comprises a coating containing a silicon-containing polymer and an organic solvent on a base film or other layers formed on the base film. A step of forming a layer containing the silicon-containing polymer by drying the coating film obtained in the step (B-1) and the step (B-1) of forming a coating film by applying a working solution. (B-2) and the step (B-3) of modifying the layer containing the silicon-containing polymer obtained in the step (B-2) to form a gas barrier layer, The coating liquid applied in the step (B-1) is supplied to the coating apparatus by the coating liquid supply method of the present invention.

In the step (B-1), a coating film is formed by applying a coating solution containing a silicon-containing polymer and an organic solvent on the base film or other layers formed on the base film. It is a process.
The base film to be used is not particularly limited as long as it has sufficient strength as a base material for the gas barrier film.
Examples of the base film include the same base materials as those shown in step (A-1), but a resin film is usually used.

  Resin components of the resin film include polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polysulfone, polyethersulfone, polyphenylene sulfide, acrylic resin, cycloolefin Examples thereof include polymers and aromatic polymers.

  Among these, since it is excellent in transparency and has versatility, polyester, polyamide or cycloolefin polymer is preferable, and polyester or cycloolefin polymer is more preferable.

Examples of the polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, and the like, and polyethylene terephthalate is preferable.
Examples of the polyamide include 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. .

  The resin film may contain various additives as long as the effects of the present invention are not hindered. Examples of the additive include an ultraviolet absorber, an antistatic agent, a stabilizer, an antioxidant, a plasticizer, a lubricant, and a coloring pigment. What is necessary is just to determine suitably content of these additives according to the objective.

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

The thickness of the base film is not particularly limited, and may be determined according to the purpose of the gas barrier film. The thickness of a base film is 0.5-500 micrometers normally, Preferably it is 1-100 micrometers.
80% or more is preferable and, as for the light transmittance in 380-780 nm of a base film, 85% or more is more preferable.

  Examples of the other layer in the step (B-1) include the same layers as those described in the step (A-1). Moreover, as a coating method of the coating liquid in a process (B-1), the thing similar to the coating method demonstrated in the process (A-1) is mentioned.

  The thickness of the coating film is not particularly limited, but is usually 20 nm to 10 μm, preferably 30 to 500 nm, more preferably 40 to 400 nm.

The step (B-2) is a step of forming a layer containing the silicon-containing polymer by drying the coating film obtained in the step (B-1).
Examples of the drying method and drying conditions in the step (B-2) include the same as those described in the step (A-1).

  Step (B-3) is a step of modifying the layer containing the silicon-containing polymer obtained in step (B-2) to form a gas barrier layer.

Examples of the method for modifying the layer containing the silicon-containing polymer include ion implantation treatment, plasma treatment, ultraviolet irradiation treatment, and heat treatment.
As will be described later, the ion implantation treatment is a method of modifying the layer containing the silicon-containing polymer by implanting ions into the layer containing the silicon-containing polymer.
The plasma treatment is a method for modifying a layer containing a silicon-containing polymer by exposing the layer containing a silicon-containing polymer to plasma. For example, plasma treatment can be performed according to a method described in Japanese Patent Application Laid-Open No. 2012-106421.
The ultraviolet irradiation treatment is a method of modifying the layer containing the silicon-containing polymer by irradiating the layer containing the silicon-containing polymer with ultraviolet rays. For example, the ultraviolet modification treatment can be performed according to the method described in JP2013-226757A.
Among these, the ion implantation treatment is preferable because the gas barrier layer can be efficiently modified to the inside without roughening the surface of the layer containing the silicon-containing polymer and more excellent in gas barrier properties.

As ions implanted into the layer containing the silicon-containing polymer, 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 and ethane; ions of alkene gases such as ethylene and propylene; ions of alkadiene gases such as pentadiene and butadiene; ions of alkyne gases such as acetylene; benzene and toluene Ions of aromatic hydrocarbon gases such as cyclopropane; ions of cycloalkane gases such as cyclopropane; ions of cycloalkene gases such as cyclopentene; ions of metals; ions of organosilicon compounds;
These ions can be used alone or in combination of two or more.
Among these, ions of rare gases such as argon, helium, neon, krypton, and xenon are preferable because ions can be implanted more easily and a gas barrier layer having better gas barrier properties can be formed.

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

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

  In the plasma ion implantation, for example, plasma is generated in an atmosphere containing a plasma generating gas such as a rare gas, and a negative high voltage pulse is applied to the layer containing the silicon-containing polymer, whereby ions in the plasma ( Cations) can be injected into the surface portion of the layer containing the silicon-containing polymer.

  By ion implantation, the thickness of the region into which ions are implanted can be controlled by the implantation conditions such as the type of ion, applied voltage, and processing time. The thickness of the layer containing the silicon-containing polymer and the purpose of use of the laminate However, it is usually 10 to 400 nm.

According to the method for producing a gas barrier film of the present invention, it is possible to obtain a gas barrier film having a gas barrier layer that hardly contains minute foreign matters.
The gas barrier film obtained by the method of the present invention is excellent in gas barrier properties.

The gas barrier film of the present invention, the temperature 40 ° C., 90% relative humidity, the water vapor permeability is preferably 0.05g ^/ (m 2 · day) less, more preferably 0.04g ^/ (m 2 · day) or less It is. There is no particular lower limit, and the lower the better, the better, but it is usually 0.001 g / (m ² · day) or more.
The water vapor transmission rate can be measured by the method described in the examples.

  Thus, since the gas barrier film of the present invention is excellent in gas barrier properties, it is suitably used as a material constituting electronic devices such as liquid crystal displays, organic EL displays, inorganic EL displays, organic EL lighting, electronic paper, and solar cells. .

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.
Unless otherwise indicated, the part and% in each example are based on mass.

[Measurement of water vapor permeability]
The water vapor permeability of the gas barrier films obtained in Examples 1 to 4 and Comparative Examples 1 to 4 was measured using a water vapor permeability measuring device (manufactured by mocon, PERMATRAN). The measurement was performed in an atmosphere of 40 ° C. and 90% relative humidity. As a result, 0.05 g / (m ² · day) or more was evaluated as x, and less than 0.05 g / (m ² · day) was evaluated as ◯.

[Surface observation]
The surfaces of the gas barrier films obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were observed using a scanning electron microscope (manufactured by Keyence Corporation, VE-9800). Presence / absence) and presence / absence of foreign matter (presence or absence of substantially spherical objects).

[Production Example 1]
200 g of polysilazane (manufactured by AZ Electronic Materials, NAX120-20, number average molecular weight: 1000) was diluted with 800 g of dibutyl ether (manufactured by AZ Electronic Materials) to obtain a coating liquid (1).

[Production Example 2]
200 g of polymethylsilsesquioxane (manufactured by Konishi Chemical Co., Ltd., PMSQ SR-13, number average molecular weight: 1000) was diluted with 800 g of toluene (manufactured by Tokyo Chemical Industry Co., Ltd.) to obtain a coating liquid (2).
[Example 1]
Using the coating liquid supply apparatus having the configuration shown in FIG. 1, the coating liquid (1) is transferred from the storage tank to the coating apparatus, and a polyethylene terephthalate film (Toyobo Co., Ltd., Cosmo Shine PET50A-4100, thickness) 50 μm) was applied to the coating solution.
The obtained coating film was heat-dried at 100 ° C. for 5 minutes using a dryer to form a polysilazane-containing layer. Subsequently, a gas barrier layer was formed on the polysilazane-containing layer by performing plasma ion implantation treatment (treatment conditions are shown below), and a gas barrier film I was obtained.
In Example 1, as a filter constituting the coating solution supply apparatus, the material is polytetrafluoroethylene (PTFE), and the pore size is 0.10 μm. Filter A (Wintec, FPF-010) Was used.

[Processing conditions for plasma ion implantation]
Chamber internal pressure: 0.2 Pa
Plasma generation gas: Argon gas flow rate: 100 sccm
RF output: 1000W
RF frequency: 1000Hz
RF pulse width: 50 μsec
RF delay: 25nsec
DC voltage: -6kV
DC frequency: 1000Hz
DC pulse width: 5 μsec
DC delay: 50 μsec
Duty ratio: 0.5%
Processing time: 200 sec

[Example 2]
In Example 1, the gas barrier film was the same as Example 1 except that the filter A was changed to the filter B (made by Wintech, FPF-022) having a material of PTFE and a pore size of 0.22 μm. II was obtained.

[Example 3]
In Example 1, the gas barrier film was the same as Example 1 except that the filter A was changed to a filter C (made by Wintech, FPF-045) made of PTFE and having a pore size of 0.45 μm. III was obtained.

[Example 4]
Example 1 is the same as Example 1 except that the filter A is changed to a filter D (made by Wintech, PODMF-045) whose material is PVDF (polyvinylidene fluoride) and the pore size is 0.45 μm. Similarly, a gas barrier film IV was obtained.

[Example 5]
In Example 3, a gas barrier film V was obtained in the same manner as in Example 3 except that the coating liquid (2) was used instead of the coating liquid (1).

[Comparative Example 1]
In Example 1, the gas barrier film VI was formed in the same manner as in Example 1 except that the filter A was changed to the filter E (made by Wintech, FPF-100) having a material of PTFE and a pore size of 1 μm. Obtained.

[Comparative Example 2]
In Example 1, the gas barrier was changed in the same manner as in Example 1 except that the filter A was changed to a filter F (manufactured by Nihon Entegris, process guard NP PNA5ADSE1) made of polypropylene and having a pore size of 0.5 μm. Film VII was obtained.

[Comparative Example 3]
Example 1 is the same as Example 1 except that the filter A is changed to a filter G (manufactured by 3M, Life ASSURE 70126-33-020ER) made of nylon 66 and having a pore size of 0.2 μm. Thus, a gas barrier film VIII was obtained.

[Comparative Example 4]
In Example 1, the gas barrier film IX was prepared in the same manner as in Example 1 except that the filter A was changed to a filter H (manufactured by 3M, Betapure AU0911070) made of polypropylene and having a pore size of 0.7 μm. Obtained.

[Comparative Example 5]
In Example 1, the filter A was changed to a filter H (manufactured by 3M, Betapure AU0911070) made of polypropylene and having a pore size of 0.7 μm, and the coating liquid was changed to the coating liquid (1). A gas barrier film X was obtained in the same manner as in Example 1 except that (2) was used.

  Table 1 shows the water vapor permeability of the gas barrier films I to X and the surface observation results.

From Table 1, the following can be understood.
In Examples 1-5, elution of the resin component of the filter and mixing of foreign matters were not confirmed, and gas barrier films excellent in gas barrier properties were obtained.
On the other hand, in Comparative Examples 1, 4 and 5 using a filter with a large pore diameter, foreign matter was confirmed, and in Comparative Examples 2 to 5 using a filter other than a fluororesin, elution of the resin component of the filter was confirmed. It was. And all the gas barrier films obtained by Comparative Examples 1-5 are inferior to gas barrier property.

1. 1. Inert gas cylinder 2. Coating liquid tank 3. Liquid feed pump Filter 5. Coating equipment

Claims (8)

A coating liquid supply apparatus for supplying a coating liquid to a coating apparatus,
A coating liquid tank for storing the coating liquid;
A liquid feed pump for transferring the coating liquid from the coating liquid tank to the coating apparatus;
A filter for filtering the coating liquid fed from the coating liquid tank;
A liquid feed pipe for connecting the coating liquid tank, a liquid feeding pump, a filter, and a coating apparatus, and feeding the coating liquid from the coating liquid tank to the coating apparatus;
With
The coating liquid supply apparatus, wherein the filter is made of a fluororesin and has a pore diameter of 0.50 μm or less. A coating liquid supply method for supplying a coating liquid containing a compound capable of high molecular weight during storage and / or liquid feeding and an organic solvent to a coating apparatus,
A coating liquid supply method comprising: supplying a coating liquid in a coating liquid tank to a coating apparatus using the coating liquid supply apparatus according to claim 1.   The coating liquid according to claim 2, wherein the compound capable of increasing the molecular weight during the storage and / or liquid feeding is a compound capable of reacting with moisture in the air during the storage and / or liquid feeding to increase the molecular weight. Supply method.   The coating liquid supply method according to claim 2 or 3, wherein the compound capable of increasing the molecular weight during storage and / or liquid feeding is a silicon-containing polymer. On the base material or other layers formed on the base material, a coating liquid is formed by applying a coating solution containing a compound capable of increasing the molecular weight during storage and / or liquid feeding and an organic solvent. The step (A-1) and the step (A) of forming a layer containing a compound capable of increasing the molecular weight during the storage and / or liquid feeding by drying the coating film obtained in the step (A-1). -2),
A method for producing a laminate having
The coating liquid applied in the step (A-1) is supplied to the coating apparatus by the coating liquid supply method according to any one of claims 2 to 4, and is a laminate having the coating liquid supplied in the step (A-1). Manufacturing method. A step (B-1) of forming a coating film by applying a coating solution containing a silicon-containing polymer and an organic solvent on the base film or other layers formed on the base film;
A step (B-2) of forming a layer containing the silicon-containing polymer by drying the coating film obtained in the step (B-1); and
A step of modifying the layer containing the silicon-containing polymer obtained in the step (B-2) to form a gas barrier layer (B-3),
A method for producing a gas barrier film comprising:
A method for producing a gas barrier film, wherein the coating liquid to be applied in the step (B-1) is supplied to a coating apparatus by the coating liquid supply method according to claim 4.   A laminate obtained by the method according to claim 5.   A gas barrier film obtained by the method according to claim 6.

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