WO2013175911A1 - Feuille barrière aux gaz et procédé de fabrication d'une feuille barrière aux gaz - Google Patents

Feuille barrière aux gaz et procédé de fabrication d'une feuille barrière aux gaz Download PDF

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WO2013175911A1
WO2013175911A1 PCT/JP2013/061570 JP2013061570W WO2013175911A1 WO 2013175911 A1 WO2013175911 A1 WO 2013175911A1 JP 2013061570 W JP2013061570 W JP 2013061570W WO 2013175911 A1 WO2013175911 A1 WO 2013175911A1
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gas barrier
barrier sheet
resin
group
sheet
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PCT/JP2013/061570
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Japanese (ja)
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悠太 鈴木
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リンテック株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/048—Forming gas barrier coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/16—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/16—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms

Definitions

  • the present invention relates to a gas barrier sheet and a method for producing the gas barrier sheet, and more particularly to a gas barrier sheet suitably used for an electronic device and an efficient method for producing such a gas barrier sheet.
  • a polymer molded body such as a plastic film is inexpensive and excellent in workability, and thus has a desired function and is used in various fields.
  • food and pharmaceutical packaging films have a gas barrier layer that prevents the permeation of water vapor and oxygen on the plastic film as a base material in order to maintain the taste and freshness by suppressing the oxidation and alteration of proteins and fats and oils.
  • a formed gas barrier plastic film is used.
  • a transparent plastic film for example, a gas barrier polyester film.
  • the optical resin sheet which has the barrier property with respect to gas, such as oxygen and water vapor
  • the manufacturing method of the gas barrier film applied to the organic EL element etc. which are easy to manufacture without using heat processing etc. is disclosed (for example, refer patent document 2). More specifically, a method for producing a gas barrier film comprising forming a polysilazane film from a polysilazane compound on at least one surface of a plastic film, and subjecting the polysilazane film to plasma treatment to form a gas barrier film. is there.
  • Patent Document 3 an optical film containing polysilazane and having heat resistance, solvent resistance, and the like has been proposed (see, for example, Patent Document 3). More specifically, it contains a photocrosslinking aromatic compound having one or more hydroxyl groups and a polysilazane compound in a predetermined ratio and irradiates polarized light thereto, whereby the hydroxyl group of the photocrosslinking aromatic compound is irradiated. And a polysilazane react to form a hybrid polymer, which is an optical film using the hybrid polymer.
  • the conventional gas barrier plastic films disclosed in Patent Documents 1 and 2 are films each having a gas barrier layer obtained by converting a polysilazane film into silica, and are excellent in predetermined barrier properties. There existed a subject that heat resistance depended on the resin film to be used. In addition, in order to prevent the gas barrier layer from being damaged and the barrier property from being deteriorated, it is necessary to separately laminate a polymer layer and a hard coat layer on the surface of the gas barrier layer, which increases the number of processes and reduces the productivity. There was a problem.
  • the optical film disclosed in Patent Document 3 uses a polysilazane compound as one of the compounding components and is excellent in heat resistance, but does not consider any gas barrier property. In addition, since it is an optical film obtained by reacting a polysilazane compound and a photocrosslinkable aromatic compound, there has been a problem that the film itself becomes hard and the flexibility is poor.
  • an object of the present invention is to provide a heat-resistant gas barrier sheet composed of a predetermined compound and an efficient method for producing such a gas barrier sheet.
  • a gas barrier sheet characterized by being subjected to plasma ion implantation treatment can be provided to solve the above-described problems. That is, according to the gas barrier sheet formed by forming a resin composition containing a silicon-containing polymer and a predetermined thermoplastic resin and then performing plasma ion implantation, excellent gas barrier properties and scratch resistance are obtained. , And good flexibility can be obtained. Moreover, when the said gas barrier sheet is used as a member for electronic devices, sufficient heat resistance can be exhibited.
  • the silicon-containing polymer is preferably a polysilazane compound.
  • a gas barrier sheet having excellent gas barrier properties can be obtained by using a polysilazane compound as the silicon-containing polymer.
  • the thermoplastic resin is preferably at least one selected from the group consisting of a polycarbonate resin, a cycloolefin resin, and a polysulfone resin.
  • a thermoplastic resin compatibility with the silicon-containing polymer is improved, and a gas barrier sheet that is further excellent in transparency in addition to gas barrier properties and heat resistance can be obtained.
  • the amount of the silicon-containing polymer is preferably set to a value in the range of 5 to 1000 parts by mass with respect to 100 parts by mass of the thermoplastic resin.
  • the plasma ion implantation process In constructing the gas barrier sheet of the present invention, the plasma ion implantation process generates plasma in an atmosphere containing a plasma generation gas, and applies a negative high voltage pulse to the surface of the processing layer. Plasma ion implantation for implanting ions therein is preferable. As described above, by performing the plasma ion implantation treatment, a gas barrier sheet having more excellent gas barrier properties can be obtained.
  • the thickness is preferably set to a value within the range of 0.5 to 500 ⁇ m.
  • Another aspect of the present invention is a method for producing a gas barrier sheet derived from a gas barrier material comprising a silicon-containing polymer and a thermoplastic resin, comprising the following steps (1) to (2): It is the manufacturing method of the gas barrier sheet characterized. (1) Step of forming a gas barrier material containing a silicon-containing polymer and a thermoplastic resin having a glass transition temperature of 100 ° C. or higher (2) Plasma ion implantation treatment for the gas barrier material formed into a sheet Step of making a gas barrier sheet by performing the above, that is, by producing a gas barrier sheet in this way, it is possible to efficiently obtain a gas barrier sheet having excellent gas barrier properties and scratch resistance, and good flexibility and durability. Can do.
  • Drawing 1 is a mimetic diagram offered in order to explain a section of a gas barrier sheet.
  • FIGS. 2A to 2E are views for explaining a method for manufacturing a gas barrier sheet.
  • Drawing 3 is a mimetic diagram offered in order to explain an example of an electronic device provided with the gas barrier sheet of the present invention.
  • FIG. 4 is a schematic diagram for explaining an example of an electronic device including the gas barrier sheet of the present invention.
  • FIG. 5 is a schematic diagram for explaining an example of an electronic device including the gas barrier sheet of the present invention.
  • the first embodiment is a gas barrier sheet derived from a gas barrier material containing a silicon-containing polymer and a thermoplastic resin, and the glass transition temperature of the thermoplastic resin is 100 ° C. or higher.
  • the gas barrier sheet 100 has been subjected to plasma ion implantation for the gas barrier material.
  • the gas barrier sheet of the first embodiment will be specifically described with reference to the drawings as appropriate.
  • the silicon-containing polymer is defined as a polymer containing a silicon atom in the molecule (including a compound containing a silicon atom). It may be a compound. Therefore, for example, at least one of a polyorganosiloxane compound, a polycarbosilane compound, a polysilane compound, a polysilazane compound, and the like can be given. Among these types, it is preferable to use a polysilazane compound as the silicon-containing polymer because it can be easily modified by plasma ion implantation treatment and can exhibit excellent gas barrier properties and scratch resistance.
  • a silazane compound in a gas barrier material film is obtained by subjecting a gas barrier material (gas barrier material film) comprising a polysilazane compound as a silicon-containing polymer and a resin composition containing a thermoplastic resin, which will be described later, to plasma ion implantation.
  • a gas barrier material gas barrier material film
  • the entire gas barrier material film is modified, and predetermined gas barrier properties and scratch resistance can be exhibited.
  • the number average molecular weight of a suitable polysilazane compound is not particularly limited, but it is usually preferably a value within the range of 100 to 50,000.
  • Such a polysilazane compound is a compound having a repeating unit containing a —Si—N— bond (silazane bond) in the molecule, and is defined as a compound having a repeating unit represented by the following general formula (1).
  • 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.
  • a non-hydrolyzable group such as an alkenyl group, an unsubstituted or substituted aryl group or an alkylsilyl group, and the subscript n represents an arbitrary natural number.
  • alkyl group of the above-described unsubstituted or substituted alkyl group examples include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group.
  • alkyl groups having 1 to 10 carbon atoms such as butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group and n-octyl group.
  • 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 the above-described unsubstituted or substituted alkenyl group include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, and a 3-butenyl group. Examples include alkenyl groups having 2 to 10 carbon atoms.
  • examples of the substituent for the alkyl group, cycloalkyl group, and alkenyl group described above include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; hydroxyl group; thiol group; epoxy group; glycidoxy group; ) Acryloyloxy group; unsubstituted or substituted aryl group such as phenyl group, 4-methylphenyl group, 4-chlorophenyl group; and the like.
  • Examples 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 for 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; methoxy group and ethoxy group Nitro group; cyano group; hydroxyl group; thiol group; epoxy group; glycidoxy group; (meth) acryloyloxy group; phenyl group, 4-methylphenyl group, 4-chlorophenyl group, etc. An unsubstituted or substituted aryl group; and the like.
  • alkylsilyl group described above examples include trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, tri-t-butylsilyl group, methyldiethylsilyl group, dimethylsilyl group, diethylsilyl group, methylsilyl group, and ethylsilyl group.
  • Rx, Ry, and Rz are preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and particularly preferably a hydrogen atom.
  • polysilazane compound examples include an inorganic polysilazane compound in which Rx, Ry, and Rz are all hydrogen atoms in the general formula (1), an organic polysilazane in which at least one of Rx, Ry, and Rz is not a hydrogen atom, or a modified polysilazane. Is mentioned.
  • examples of such inorganic polysilazane compounds include compounds having structures represented by the following general formulas (2) to (3) and formula (4).
  • perhydropolysilazane having a linear structure and a branched structure having a repeating unit represented by the following general formula (3) can be mentioned as a suitable silicon-containing polymer.
  • Y 1 is a hydrogen atom or a group represented by the following general formula (3 ′), and subscripts c and d each represent an arbitrary natural number.
  • Y 2 is a hydrogen atom or a group represented by General Formula (3 ′), subscript e represents an arbitrary natural number, and * represents a bonding position.
  • perhydropolysilazane having a perhydropolysilazane structure represented by the following formula (4) and having a linear structure, a branched structure and a cyclic structure in the molecule can be mentioned.
  • An organic polysilazane compound in which at least one of Rx, Ry, and Rz in the general formula (1) is not a hydrogen atom but an organic group is also suitable.
  • Examples of the organic polysilazane compound include compounds having structures represented by the following general formulas (5) to (7), the following formula (8), and the general formula (9).
  • Rx ′ has an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted group.
  • Rz ′ represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, or an alkylsilyl group.
  • Ry ′ has an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted group.
  • Y 3 is a hydrogen atom or a group represented by the following general formula (9 ′), and the subscripts f and g represent arbitrary natural numbers.
  • Y 4 represents a hydrogen atom or a group represented by general formula (9 ′), subscript h represents an arbitrary natural number, and * represents a bonding position.
  • the organic polysilazane compound mentioned above can be manufactured by a well-known method.
  • it can be obtained by reacting ammonia or a primary amine with the reaction product of an unsubstituted or substituted halogenosilane compound represented by the following general formula (10) and a secondary amine.
  • the secondary amine, ammonia, and primary amine to be used can be suitably selected according to the structure of the target polysilazane compound.
  • X represents a halogen atom
  • R 1 is a substituent of any one of Rx, Ry, Rz, Rx ′, Ry ′ and Rz ′ described above, and m is 1 to 3) Is an integer.
  • modified polysilazane as the polysilazane compound.
  • modified polysilazane include a polymetallosilazane containing a metal atom (the metal atom may be crosslinked), and repeating units of [(SiH 2 ) i (NH) j ] and [(SiH 2 ). k O] (subscripts i, j and k are each independently 1, 2 or 3).
  • Polyborosilazane, polysilazane and metal alkoxide produced by reacting a boron compound with polysiloxazan or polysilazane.
  • Ceramicized polysilazane, silicon alkoxide-added polysilazane, glycidol-added polysilazane Silazanes, acetylacetonato complexes addition polysilazane include metal carboxylate added polysilazane.
  • a polysilazane composition obtained by adding amines and / or acids to the above-described polysilazane compound or a modified product thereof, obtained by adding alcohol such as methanol or hexamethyldisilazane to a terminal N atom to perhydropolysilazane.
  • Thermoplastic resin used in the present invention is a polymer material having a glass transition temperature (Tg) of 100 ° C. or higher. This is because a gas barrier sheet having excellent gas barrier properties and heat resistance can be obtained with a thermoplastic resin having such a glass transition temperature. Accordingly, the thermoplastic resin is more preferably a polymer material having a glass transition temperature of 140 ° C. or higher.
  • the glass transition temperature of the thermoplastic resin can be measured by viscoelasticity measurement. More specifically, the temperature showing the maximum value of Tan ⁇ (loss elastic modulus / storage elastic modulus) obtained by viscoelasticity measurement. Is defined.
  • the thermoplastic resin is preferably an amorphous thermoplastic resin. This is because a gas barrier film that is superior in transparency can be obtained if it is an amorphous thermoplastic resin. Moreover, since an amorphous thermoplastic resin is easy to melt
  • the amorphous thermoplastic resin means a thermoplastic resin whose melting point is not observed in the differential scanning calorimetry.
  • the weight average molecular weight (Mw) of the thermoplastic resin is usually preferably a value in the range of 100,000 to 3,000,000, and a value in the range of 200,000 to 2,000,000. More preferably, the value is more preferably in the range of 500,000 to 2,000,000.
  • the molecular weight distribution (Mw / Mn) is preferably set to a value in the range of 1.0 to 5.0, and more preferably set to a value in the range of 2.0 to 4.5.
  • a weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) can be calculated as a polystyrene conversion value by a gel permeation chromatography (GPC) method.
  • thermoplastic resin is not particularly limited.
  • polysulfone resin, polyarylate resin, polycarbonate resin, polyimide resin, polyamide resin, polyamideimide resin, and cycloolefin resin are more preferable because of excellent heat resistance and transparency and versatility.
  • Polysulfone resin Resins, polycarbonate resins and cycloolefin resins are particularly preferred.
  • Gas barrier material includes at least the silicon-containing polymer and the thermoplastic resin described above, and after forming the gas barrier material, a predetermined gas barrier sheet can be obtained by plasma ion implantation treatment. it can.
  • the blending amount of the silicon-containing polymer is preferably set to a value within the range of 5 to 1000 parts by mass with respect to 100 parts by mass of the thermoplastic resin.
  • the reason for this is that excellent gas barrier properties, heat resistance, scratch resistance, and flexibility of the gas barrier sheet can be obtained by using such a blending amount. More specifically, when the amount of the silicon-containing polymer is less than 5 parts by mass, gas barrier properties, heat resistance, and scratch resistance may decrease. On the other hand, when the blending amount of the silicon-containing polymer exceeds 1000 parts by mass, the flexibility of the gas barrier sheet may be lowered.
  • the blending amount of the silicon-containing polymer is preferably set to a value within the range of 10 to 500 parts by weight, and more preferably within a range of 20 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin. Is more preferable.
  • the gas barrier material can contain other components within a range that does not impair the object and effect of the present invention.
  • other components include at least one of an antioxidant, a UV absorber, a plasticizer, an energy ray curable resin, and a thermosetting resin such as an epoxy resin.
  • the gas barrier material can be prepared, for example, by mixing a silicon-containing polymer, a thermoplastic resin, and other components as desired, and dissolving or dispersing them in a suitable solvent as necessary.
  • the solvent to be used is not particularly limited as long as it can dissolve or disperse the silicon-containing polymer and the thermoplastic resin.
  • aliphatic hydrocarbon solvents such as n-hexane and n-heptane
  • alicyclic hydrocarbon solvents such as cyclopentane and cyclohexane
  • aromatic hydrocarbon solvents such as toluene and xylene
  • Halogenated hydrocarbon solvents such as ethylene and dichloromethane
  • alcohol solvents such as methanol, ethanol, propanol, butanol and propylene glycol monomethyl ether
  • ketone solvents such as acetone, methyl ethyl ketone, 2-pentanone, isophorone and cyclohexanone
  • ethyl acetate examples thereof include ester solvents such as butyl acetate; cellosolv solvents such as ethyl cellosolve; ether solvents such
  • Gas Barrier Sheet (1) Gas Barrier Sheet
  • the gas barrier sheet of the present invention is formed by plasma ion implantation after forming the gas barrier material.
  • Such a gas barrier sheet is preferably used as a member for an electronic device because it has excellent gas barrier properties, scratch resistance, flexibility, and sufficient heat resistance.
  • such a gas barrier sheet is subjected to plasma ion implantation treatment, whereby a film made of a gas barrier material is modified and exhibits excellent gas barrier properties. be able to.
  • the plasma ion implantation process will be described in detail in a second embodiment described later.
  • the thickness of the gas barrier sheet may be determined in accordance with the purpose of the gas barrier sheet, but it is usually preferable to set a value within the range of 0.5 to 500 ⁇ m. The reason for this is that when the thickness of the gas barrier sheet is less than 0.5 ⁇ m, the mechanical strength decreases and the handleability decreases. On the other hand, when the thickness of the gas barrier sheet exceeds 500 ⁇ m, it is flexible and transparent. This is because there is a case where the property is lowered. Accordingly, the thickness of the gas barrier sheet is more preferably set to a value within the range of 1.0 to 100 ⁇ m, and further preferably set to a value within the range of 2 to 50 ⁇ m. Yes.
  • the water vapor permeability of the gas barrier sheet is preferably a value of 1.0 g / (m 2 ⁇ day) or less, and is a value within the range of 0.01 to 1.0 g / (m 2 ⁇ day). It is more preferable that the value be in the range of 0.01 to 0.5 g / (m 2 ⁇ day). The reason for this is that if the value of the water vapor transmission rate is in the above range, the gas barrier property is excellent, so that it can be suitably used as a gas barrier sheet for an electronic member.
  • the water vapor transmission rate of the gas barrier sheet can be measured by a known method, for example, preferably measured according to JIS K 7129 or JIS Z 0208.
  • the gas barrier sheet of this invention comes to show abrasion resistance. And whether or not the gas barrier sheet has scratch resistance can be determined by measuring the surface hardness measured with the nanoindenter of the gas barrier sheet, and is usually 2.0 GPa or more, Since it has excellent scratch resistance, it can be suitably used as a gas barrier sheet for electronic members. Whether the gas barrier sheet has predetermined heat resistance can be determined by measuring the glass transition temperature of the gas barrier sheet. Therefore, normally, if it is 100 degreeC or more, since it is excellent in heat resistance, it can be used suitably as a gas barrier sheet for electronic members.
  • the gas barrier sheet of the present invention preferably has a single layer structure, but other layers may be further laminated.
  • the other layer may be a single layer or a plurality of layers.
  • the other layer may be formed on both surfaces of the gas barrier sheet, and may be formed on one surface.
  • examples of such other layers include inorganic compound layers, conductor layers, hard coat layers, refractive index adjustment layers, light diffusion layers, easy adhesion layers, antiglare treatment layers, pressure-sensitive adhesive layers, gas barrier layers, and polyolefin films.
  • resin films other than the present invention such as a polyvinyl chloride film and a polyethylene terephthalate film.
  • an inorganic compound layer is a layer which consists of a 1 type, or 2 or more types of combination of an inorganic compound, it is also preferable to attach this inorganic compound layer with a gas barrier sheet.
  • an inorganic compound which comprises an inorganic compound layer it can generally form into a vacuum and has a gas barrier property, for example, an inorganic oxide, an inorganic nitride, an inorganic carbide, an inorganic sulfide, and these composites. Examples thereof include inorganic oxynitrides, inorganic oxycarbides, inorganic nitriding carbides, and inorganic oxynitriding carbides.
  • the conductor layer is a layer for imparting a conductivity of 1 to 1000 ⁇ / ⁇ , an antistatic property or the like as a sheet resistance to the gas barrier sheet. It is preferable to add to the side.
  • a material which comprises a conductor layer a metal, an alloy, a metal oxide, an electroconductive compound, a mixture thereof, etc. are mentioned. More specifically, antimony-doped tin oxide (ATO); fluorine-doped tin oxide (FTO); 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 Examples thereof include conductive materials.
  • the hard coat layer is a layer provided for the purpose of imparting antifouling property or for further improving the scratch resistance.
  • a hard coat layer is formed, for example, by forming a cured film on the surface of the gas barrier sheet of the present invention using an ultraviolet curable resin such as a silicone resin, a urethane resin, an acrylic resin, or an epoxy resin. can get.
  • the refractive index adjustment layer is a layer provided for controlling reflection. Therefore, the refractive index adjustment layer can be formed using a high refractive material or a low refractive material so that desired performance can be obtained.
  • the easy-adhesion layer is a layer provided in order to improve surface adhesion. And such an easily bonding layer can be formed by a conventionally well-known method.
  • the light diffusion layer is a layer provided for diffusing light, and the viewing angle can be expanded when the gas barrier sheet of the present invention is used in a liquid crystal display device or the like.
  • a light diffusion layer can be formed by a conventionally known method.
  • the antiglare treatment layer is a layer provided for the purpose of preventing visual interference of transmitted light due to reflection of external light.
  • Such an antiglare layer can be formed by a conventionally known method using a coating agent containing a filler such as silica particles.
  • the pressure-sensitive adhesive layer is a layer for imparting pressure-sensitive adhesive properties.
  • known pressure-sensitive adhesives such as acrylic pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, polyurethane-based pressure-sensitive adhesives, and silicone-based pressure-sensitive adhesives are used. This method can be used.
  • gas barrier sheet of the present invention is excellent in gas barrier properties, scratch resistance, and flexibility, and has sufficient heat resistance. Therefore, sealing of resin substrates for electronic devices such as liquid crystal display elements, electronic paper, organic EL elements, organic thin film solar cells, back sheets or front sheets for solar cells, organic EL elements and organic thin film solar elements It can be suitably used for a sheet or the like.
  • FIGS. 3 to 5 the electronic device shown in FIGS. 3 to 5 will be described as an example of an electronic device including the gas barrier sheet of the present invention.
  • the gas barrier sheet 100 of the present invention when used as a resin substrate, the electronic device 2 has a transparent second electrode 13 such as ITO on the gas barrier sheet 100 as shown in FIG.
  • An organic functional layer 14 is provided on the electrode 13, and a first electrode 15 is provided on the organic functional layer 14.
  • the gas barrier sheet 100 of this invention as a sealing sheet, as shown in FIG.
  • the electronic device 22 has the 2nd electrode 13 on the board
  • a first electrode 15 is provided on the organic functional layer 14, and a gas barrier sheet 100 is provided on the first electrode 15.
  • the electronic device 222 has the second electrode 13 on the gas barrier sheet 100 as a resin base material.
  • the organic functional layer 14 is provided on the second electrode 13, the first electrode 15 is provided on the organic functional layer 14, and the gas barrier sheet 100 as a sealing sheet is provided on the first electrode 15. .
  • organic functional layer 14 an organic light emitting layer, an organic photoelectric conversion layer, a liquid crystal polymer layer, etc. can be mentioned without limitation.
  • the substrate 16 in FIG. 4 include a glass substrate.
  • the second embodiment is a method for producing a gas barrier sheet derived from a gas barrier material containing a silicon-containing polymer and a thermoplastic resin, and includes the following steps (1) to (2): It is a manufacturing method of a gas barrier sheet.
  • Step of forming a gas barrier material containing a silicon-containing polymer and a thermoplastic resin having a glass transition temperature of 100 ° C. or higher (2) Plasma ion implantation for the gas barrier material formed into a sheet Process to make a gas barrier sheet by processing
  • step (1) a gas barrier material containing a silicon-containing polymer and a thermoplastic resin having a glass transition temperature of 100 ° C. or higher is formed into a resin layer (a resin layer made of a sheeted gas barrier material). It is a process to do. Therefore, the film forming method is not particularly limited, and a conventionally known method such as a casting method can be employed. However, it is more preferable to use the solution casting method because the thickness can be formed more accurately. Therefore, the method for producing the gas barrier sheet of the present invention by the solution casting method will be described below as an example.
  • a process sheet 12 is prepared as shown in FIG. 2 (a). As shown in FIG.
  • the coating method is not particularly limited, and a known method can be used.
  • a known coating method such as a fountain die method, a knife coating method, a roll coating method, a die coating method, or a spin coating method can be used.
  • the drying method in particular of the obtained resin layer is not restrict
  • Process (2) Next, as shown in FIG. 2C, in the step (2), the resin layer 10 obtained in the step (1) is subjected to plasma ion implantation treatment as represented by an arrow P, This is a step of modifying the resin layer. As a result, a gas barrier sheet 100 is formed on the process sheet 12 as shown in FIG. 2D, and finally the process barrier 12 is removed as shown in FIG. A sheet 100 is obtained.
  • the plasma ion implantation process may be performed on one surface of the resin layer 10 or may be performed on both surfaces. A known method can be used as a plasma ion implantation method.
  • 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 surface of the resin layer to cause ions in the plasma.
  • a plasma generation gas such as a rare gas
  • a negative high-voltage pulse is applied to the surface of the resin layer to cause ions in the plasma.
  • a method in which ions existing in plasma generated using an external electric field are implanted into the resin layer, or a negative high voltage applied to the resin layer without using an external electric field is preferable.
  • the ion species implanted into the resin layer is not particularly limited, but ions of rare gases such as argon, helium, neon, krypton, xenon; fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, Ions such as sulfur; ions of alkane gases such as methane, ethane, propane, butane, pentane and hexane; ions of alkenes such as ethylene, propylene, butene and pentene; alkadienes such as pentadiene and butadiene Ions of alkyne gases such as acetylene and methylacetylene; ions of aromatic hydrocarbon gases such as benzene, toluene, xylene, indene, naphthalene and phenanthrene; cycloalkane gases such as cyclopropane and cyclohe
  • the step of forming the resin layer is not limited to the solution casting method, and a conventionally known method such as extrusion molding can be employed.
  • thermoplastic resins used in advance in Examples and Comparative Examples are shown below.
  • Example 1 Adjustment of gas barrier material Polycarbonate resin A as a thermoplastic resin, 100 parts by weight of toluene is dissolved in 400 parts by mass of toluene, and a silicon-containing polymer as a main component is perhydropolysilazane (manufactured by AZ Electronic Materials, “ AZNL110-20 ", solid content concentration 20%) 500 parts by weight (that is, solid content concentration 100 parts by weight) was added to prepare a gas barrier material (concentration 10%).
  • AZ Electronic Materials “ AZNL110-20”
  • Step 1 As a process sheet, a polyethylene terephthalate film (“PET38 T-100”, thickness 38 ⁇ m, manufactured by Mitsubishi Plastics) coated with a silicone release agent was prepared. Next, the gas barrier material is applied to the process sheet in a fountain die method so that the thickness after drying becomes 5 ⁇ m, and the obtained coating film is heated at 70 ° C. for 2 minutes and then at 140 ° C. for 2 minutes, The resin layer was formed by drying.
  • PET38 T-100 thickness 38 ⁇ m, manufactured by Mitsubishi Plastics
  • Step 2 Plasma ion implantation was performed on the resin layer on the process sheet using the plasma ion implantation apparatus under the following conditions. Subsequently, the process sheet
  • Plasma generation gas Argon gas flow rate: 100 sccm RF output: 1000W RF frequency: 1000Hz RF pulse width: 50 ⁇ sec RF delay: 25nsec DC voltage: -10kV DC frequency: 1000Hz DC pulse width: 5 ⁇ sec DC delay: 50 ⁇ sec Duty ratio: 0.5% Processing time: 300 sec
  • the obtained gas barrier sheet was measured using a viscoelasticity measuring device (manufactured by TA Instruments, DMA Q800) at a frequency of 11 Hz and a temperature increase of 3 ° C./min.
  • the viscoelasticity in the tensile mode was measured in the range, and the temperature at the maximum point of tan ⁇ (loss elastic modulus / storage elastic modulus) obtained by this measurement was defined as the glass transition temperature (Tg).
  • Tg glass transition temperature
  • Table 1 also shows the glass transition temperature (Tg) measured in the same manner for the base films used in Comparative Examples 1 to 8.
  • the obtained gas barrier sheet was left to stand for 168 hours in an 80 degreeC thermostat, the state of the gas barrier sheet was observed visually, and heat resistance was evaluated as follows. ⁇ : No change is observed at all. X: Change (whitening, surface roughness, deformation) of the gas barrier sheet due to heat is recognized.
  • the scratch resistance of the gas barrier sheet was determined by measuring the surface hardness of the gas barrier sheet and evaluating the scratch resistance as follows. ⁇ : 2.0 GPa or more. X: Less than 2.0 GPa.
  • the surface hardness of the gas barrier sheet obtained by the Example and the comparative example was calculated
  • the obtained gas barrier sheet was measured for water vapor transmission rate under conditions of RH 90%, 40 ° C. using a water vapor transmission rate measuring device (manufactured by MOCON Co., Ltd., AQUATRAN). The gas barrier properties were evaluated. Further, for the evaluation of flexibility, the obtained gas barrier sheet was folded in half at the center portion, and a laminator (manufactured by Fuji Plastic Co., “LAMIPACKER LPC1502”) between two rolls was laminated at a laminating speed of 5 m / min and a temperature of 23 ° C. After passing under the conditions, the water vapor transmission rate was measured in the same manner as described above to evaluate the bending resistance.
  • a laminator manufactured by Fuji Plastic Co., “LAMIPACKER LPC1502
  • Example 2 to 7 gas barrier sheets were prepared and evaluated in the same manner as in Example 1 except that the resins and the formulations shown in Table 1 were used.
  • Comparative Example 1 In Comparative Example 1, a gas barrier sheet was prepared and evaluated in the same manner as in Example 1 except that plasma ion implantation treatment was not performed.
  • Comparative Example 2 Plasma ion implantation was performed in the same manner as in Example 1 except that no silicon-containing polymer was blended, and a gas barrier sheet was prepared and evaluated.
  • Comparative Example 3 In Comparative Example 3, a gas barrier sheet was prepared and evaluated in the same manner as in Example 1 except that the silicon-containing polymer was not blended and plasma ion implantation was not performed.
  • the gas barrier sheets of the examples have low water vapor permeability before and after the bending test, excellent gas barrier properties and flexibility, good scratch resistance, and heat resistance. It was done.
  • the gas barrier sheet of the present invention is a resin substrate for electronic devices such as electronic paper, organic electroluminescence elements, liquid crystal display devices, organic thin film solar cells, back sheets or front sheets for solar cells, organic EL elements and organic It is expected to be used effectively in various applications such as a sealing sheet for thin film solar cell elements.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne une feuille qui présente d'excellentes propriétés de barrière aux gaz, une excellente résistance aux rayures et une excellente flexibilité et qui a une résistance à la chaleur suffisante pour servir d'élément pour dispositifs électroniques ; l'invention concerne également un procédé de fabrication efficace pour une telle feuille et un dispositif électronique comportant une telle feuille. Cette feuille est une feuille barrière aux gaz issue d'une matière barrière aux gaz comprenant un polymère contenant du silicium et une résine thermoplastique. La feuille barrière aux gaz est caractérisée en ce que : la température de transition vireuse de la résine thermoplastique est d'au moins 100°C ; et la matière barrière aux gaz est soumise à une injection d'ions plasma. Le polymère contenant du silicium est un composé polysilazane. La résine thermoplastique est au moins l'une choisie dans le groupe consistant en résine de polycarbonate, résine de cyclooléfine et résine de polysulfone.
PCT/JP2013/061570 2012-05-21 2013-04-19 Feuille barrière aux gaz et procédé de fabrication d'une feuille barrière aux gaz WO2013175911A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010107018A1 (fr) * 2009-03-17 2010-09-23 リンテック株式会社 Article moulé, procédé de fabrication de l'article moulé, élément pour dispositif électronique et dispositif électronique
WO2012023389A1 (fr) * 2010-08-20 2012-02-23 リンテック株式会社 Moulage, son procédé de fabrication, pièce pour dispositifs électroniques et dispositif électronique
WO2012039355A1 (fr) * 2010-09-21 2012-03-29 リンテック株式会社 Film formant une barrière contre les gaz, procédé de fabrication associé, élément pour dispositifs électroniques, et dispositif électronique
WO2012039357A1 (fr) * 2010-09-21 2012-03-29 リンテック株式会社 Corps formé, son procédé de production, élément de dispositif électronique et dispositif électronique
WO2012039387A1 (fr) * 2010-09-21 2012-03-29 リンテック株式会社 Corps formé, procédé de fabrication associé, élément pour dispositifs électroniques et dispositif électronique

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010107018A1 (fr) * 2009-03-17 2010-09-23 リンテック株式会社 Article moulé, procédé de fabrication de l'article moulé, élément pour dispositif électronique et dispositif électronique
WO2012023389A1 (fr) * 2010-08-20 2012-02-23 リンテック株式会社 Moulage, son procédé de fabrication, pièce pour dispositifs électroniques et dispositif électronique
WO2012039355A1 (fr) * 2010-09-21 2012-03-29 リンテック株式会社 Film formant une barrière contre les gaz, procédé de fabrication associé, élément pour dispositifs électroniques, et dispositif électronique
WO2012039357A1 (fr) * 2010-09-21 2012-03-29 リンテック株式会社 Corps formé, son procédé de production, élément de dispositif électronique et dispositif électronique
WO2012039387A1 (fr) * 2010-09-21 2012-03-29 リンテック株式会社 Corps formé, procédé de fabrication associé, élément pour dispositifs électroniques et dispositif électronique

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