WO2009128270A1 - ガスバリア性組成物、コーティング膜およびそれらの製造方法、ならびに積層体 - Google Patents
ガスバリア性組成物、コーティング膜およびそれらの製造方法、ならびに積層体 Download PDFInfo
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- WO2009128270A1 WO2009128270A1 PCT/JP2009/001764 JP2009001764W WO2009128270A1 WO 2009128270 A1 WO2009128270 A1 WO 2009128270A1 JP 2009001764 W JP2009001764 W JP 2009001764W WO 2009128270 A1 WO2009128270 A1 WO 2009128270A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
- C08L101/14—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity the macromolecular compounds being water soluble or water swellable, e.g. aqueous gels
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
- C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
- C09D1/04—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates with organic additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
- B32B2307/7244—Oxygen barrier
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/008—Additives improving gas barrier properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/057—Metal alcoholates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
Definitions
- the present invention relates to a gas barrier composition, a coating film, a production method thereof, and a laminate.
- Various properties such as strength, transparency, and moldability are required for packaging resin films.
- the gas barrier property is listed as an important required performance for long-term storage of contents.
- Some resin films have a gas barrier property even with a single composition resin, but if a higher gas barrier property is required, a resin layer for further improving the gas barrier property is laminated on these resin films.
- Resin film is used.
- resins used for improving gas barrier properties include polyvinylidene chloride (PVDC), which is a chlorinated resin, and polyvinyl alcohol (PVA), which is a water-soluble polymer having a hydroxyl group, but PVDC is incinerated.
- PVA is a non-chlorine resin and has excellent performance in the dry state with respect to gas barrier properties.
- PVA has a problem that the gas barrier properties decrease when moisture is absorbed, and is not suitable for packaging of foods containing a lot of moisture. .
- the properties required for the resin film generally include, for example, the following.
- water resistance water-insoluble
- gas barrier properties In order to improve the water resistance of PVA and improve the humidity dependency of gas barrier properties, several methods for crosslinking PVA and poly (meth) acrylic acid by an esterification reaction have been proposed.
- Patent Document 1 a method of heat-treating a solution comprising PVA and poly (meth) acrylic acid, for example, in Patent Document 2, monovalent metal salts such as PVA, poly (meth) acrylic acid and hypophosphite
- Patent Document 3 an aqueous solution comprising PVA and a partially neutralized product of polyacrylic acid or polymethacrylic acid is coated on a film, heat treated, and then immersed in a solution containing a metal.
- a method has been proposed. In these methods, a hydroxyl group of PVA and a carboxyl group of poly (meth) acrylic acid are reacted to improve gas barrier properties and water resistance.
- Patent Document 4 there is also proposed a method of coating a film with an aqueous solution to which a crosslinking material such as an isocyanate compound is added in addition to PVA and polyacrylic acid, and heat-treating the film.
- a crosslinking material such as an isocyanate compound
- Patent Document 5 as another approach for improving the humidity dependence of the gas barrier, a composite coating composed of PVA, poly (meth) acrylic acid, and metal oxide obtained by hydrolysis and dehydration condensation of metal alkoxide. has been proposed.
- This film has a high gas barrier property under high humidity, and can be used as a boil or retort sterilization packaging material.
- Patent Document 6 discloses that a gas barrier coating film can be obtained by heat-treating a gas barrier composition containing a specific amount of metal alkoxide and / or a hydrolysis condensate of metal alkoxide.
- gas barrier properties and scratch resistance are improved.
- this coating film also has room for improvement in terms of suppressing deterioration of gas barrier properties under high temperature and high humidity conditions.
- the present invention has been made in view of the above circumstances, and provides a gas barrier composition capable of obtaining a film in which deterioration of gas barrier properties under high temperature and high humidity conditions is suppressed.
- the present inventors have carried out hydrolysis condensation of a water-soluble polymer (X), a water-soluble polymer having a carboxyl group (B), a metal alkoxide and / or a metal alkoxide. It is found that a coating film having a high gas barrier property can be obtained under a high temperature and high humidity condition by heat-treating the gas barrier composition comprising the product (C) and the esterification catalyst (E) as a main component. It came to complete.
- the weight ratio of the component (A) to the component (B) is 97/3 to 3/97, With respect to 100 parts by weight of the mixture of the component (A) and the component (B), the component (C) is 460 parts by weight to 1600 parts by weight, and the component (E) is 0.01 parts by weight to 100 parts by weight.
- the gas barrier composition according to (1) comprising not more than parts by weight.
- the gas barrier composition according to (1) comprising 0.1 to 20 parts by weight of the component (D) with respect to 100 parts by weight of the water-soluble polymer (X).
- the gas barrier composition according to (2) comprising 0.1 to 20 parts by weight of the component (D) with respect to 100 parts by weight of the mixture of the component (A) and the component (B).
- the functional group capable of forming a bond with the metal oxide is one or more groups selected from the group consisting of an alkoxysilyl group, a silanol group, a hydroxyl group, a carboxyl group, an amino group, and an ammonium group
- the functional group capable of forming a bond with a carboxyl group is one or more groups selected from the group consisting of an amino group, an epoxy group, a thiol group, a hydroxyl group, a urethane bonding group, a urea bonding group, and an ammonium group (3) or The gas barrier composition according to (4).
- component (D) is at least one selected from the group consisting of 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane.
- the component (E) is a metal salt of an inorganic acid, a metal salt of an organic acid, an organic phosphorus compound, a carboxylic acid and its derivative, a sulfonic acid and its derivative, an organic ammonium salt or pyridinium salt of a mineral acid, a cyano group
- the organic compound, organic compound containing isocyano group, ketene derivative, dichalcogenide compound, cyanuric chloride, carbonyldiimidazole, and one or more compounds selected from the group consisting of hexachloroacetone are described in any one of (1) to (7) Gas barrier composition.
- component (A) is one or more compounds selected from the group consisting of polyvinyl alcohol, ethylene-vinyl alcohol copolymer, and saccharides. Composition.
- the component (C) is at least one selected from the group consisting of an alkoxysilane condensate, an alkoxyzirconium condensate, an alkoxyaluminum condensate, and an alkoxytitanium condensate. Gas barrier composition.
- the component (A) is one or more compounds selected from the group consisting of polyvinyl alcohol, ethylene-vinyl alcohol copolymer, and saccharides
- the component (B) is poly (meth) acrylic acid or a partially neutralized product thereof
- (16) It further includes a compound (D) having one or more functional groups capable of forming a bond with a metal oxide and one or more functional groups capable of forming a bond with a carboxyl group in one molecule,
- the component (A) is polyvinyl alcohol
- the component (B) is polyacrylic acid
- the component (C) is tetramethoxysilane
- a water-soluble polymer (A) having a hydroxyl group a water-soluble polymer (B) having a carboxyl group, a metal alkoxide and / or a hydrolysis-condensation product (C) thereof, and an esterification catalyst (E)
- a method for producing a gas barrier composition comprising: Formulated so that the weight ratio of the component (A) and the component (B) is 97/3 to 3/97, and with respect to 100 parts by weight of the mixture of the component (A) and the component (B), The component (C) is added in an amount of 460 parts by weight or more and 1600 parts by weight or less, and the component (E) is added in an amount of 0.01 parts by weight or more and 100 parts by weight or less.
- the manufacturing method of the gas-barrier composition as described in (21) including the process of mixing a component, the said (B) component, the said (C) component, and the said (E) component.
- the step of mixing the water-soluble polymer (X), the component (C) and the component (E) includes: Mixing the water-soluble polymer (X) with the component (E) and the component (C), The gas barrier according to (21), wherein in the step of mixing the water-soluble polymer (X), the component (E) and the component (C), a hydrolysis condensation reaction of the component (C) proceeds.
- Method for producing a composition includes: Mixing the water-soluble polymer (X) with the component (E) and the component (C), The gas barrier according to (21), wherein in the step of mixing the water-soluble polymer (X), the component (E) and the component (C), a hydrolysis condensation reaction of the component (C) proceeds.
- the oxygen permeability of the coating film having a film thickness of 0.7 ⁇ m after being left for 24 hours under conditions of a temperature of 40 ° C. and a humidity of 90% is 30 cc / m 2 ⁇ day ⁇ atm or less. Coating film.
- a laminate comprising at least one coating film according to (32) or (33).
- the laminate according to (34), comprising a plastic substrate, a vapor deposition film made of an inorganic compound formed on the plastic substrate, and the coating film formed on the vapor deposition film.
- the present invention can provide a gas barrier composition capable of obtaining a film in which deterioration of gas barrier properties under high temperature and high humidity conditions is suppressed.
- the “water-soluble polymer having a hydroxyl group (A)” does not have a carboxyl group
- the “water-soluble polymer having a carboxyl group (B)” does not have a hydroxyl group.
- the gas barrier property (for hard coat) composition of the present invention is: (I) a mixture of a water-soluble polymer (A) having a hydroxyl group and a water-soluble polymer (B) having a carboxyl group, And (ii) a water-soluble polymer (AB) having a hydroxyl group and a carboxyl group A water-soluble polymer (X) containing at least one of A metal alkoxide and / or a hydrolysis condensate thereof (C); An esterification catalyst (E).
- the gas barrier property (for hard coat) composition of the present invention is: A water-soluble polymer (A) having a hydroxyl group; A water-soluble polymer (B) having a carboxyl group; A metal alkoxide and / or a hydrolysis condensate thereof (C); An esterification catalyst (E); It is preferable to contain.
- This gas barrier composition is suitably used as a coating composition.
- a coating film (hard coat) can be obtained by using the gas barrier composition of the present invention.
- the coating film in the present invention is a film coated with the gas barrier composition of the present invention, and has a layered structure having gas barrier properties.
- the gas barrier property refers to blocking oxygen, water vapor, and other gases that promote quality deterioration of the material to be coated.
- packaging materials such as food and medical care and electronic materials are required to have excellent oxygen gas barrier properties.
- the gas barrier property of the coating film was evaluated by measuring the oxygen permeability of the coating film. Furthermore, in the coating film obtained from the gas barrier composition of the present invention, deterioration of the gas barrier property under high temperature and high humidity conditions is suppressed.
- gas barrier composition the coating film, the production method thereof, and the laminate including the coating film of the present invention will be specifically described.
- the components of the gas barrier composition will be described.
- Water-soluble polymer (X) used in the present invention includes “(i) a mixture of a water-soluble polymer (A) having a hydroxyl group and a water-soluble polymer (B) having a carboxyl group”, and “(ii) a hydroxyl group. And a water-soluble polymer (AB) having a carboxyl group ”.
- the water-soluble polymer (X) in the present invention includes the following embodiments (a) to (e).
- E Water-soluble polymer (A) and water-soluble polymer (B) and water-soluble polymer (AB) mixture
- “(a) hydroxyl group It is preferable to use “a mixture of the water-soluble polymer (A) having a water-soluble polymer (B) having a carboxyl group”.
- the water-soluble polymer (A) having a hydroxyl group used in the present invention is a water-soluble polymer containing at least two hydroxyl groups in the polymer chain, Preferably, it is one or more compounds selected from the group consisting of polyvinyl alcohol, copolymers containing polyvinyl alcohol such as ethylene-vinyl alcohol copolymer, celluloses and other saccharides. These may be used alone or in combination of two or more.
- Polyvinyl alcohol has at least two or more vinyl alcohol units in the molecule, and may be a single polymer of vinyl alcohol or a copolymer containing other monomer units.
- Polyvinyl alcohol which is a single polymer, is a method of completely or partially saponifying polymers of vinyl esters such as vinyl formate, vinyl acetate, and vinyl propionate.
- the copolymer includes the above vinyl ester and an olefin having 2 to 30 carbon atoms such as ethylene, propylene and 1-butene, for example, an unsaturated nitrile having 3 to 30 carbon atoms such as acrylonitrile and methacrylonitrile.
- a copolymer with a vinyl ether having 3 to 30 carbon atoms such as methyl vinyl ether and ethyl vinyl ether can be obtained by a method such as complete or partial saponification.
- the water-soluble polymer (A) having a hydroxyl group used in the present invention for example, saccharides can be used. Oligosaccharides and polysaccharides can be used as the saccharides.
- the oligosaccharide refers to a substance having a sugar polymerization degree of 2 or more and 10 or less. Examples of oligosaccharides include sucrose, maltose, isomaltose, cellobiose, and lactose. Oligosaccharides can be used alone or in combination of two or more.
- the polysaccharide refers to a high molecular compound having a sugar polymerization degree of 10 or more.
- polysaccharide examples include starch, glycogen, cellulose, pectin, hemicellulose, pectic acid, alginic acid, carrageenan, agarose and the like. Polysaccharides can be used alone or in combination of two or more.
- water-soluble polymers (A) having a hydroxyl group one or more compounds selected from the group consisting of polyvinyl alcohol, ethylene-vinyl alcohol copolymer, and saccharide are preferable.
- the degree of saponification is preferably closer to 100% from the viewpoint of gas barrier properties, but is usually 90% or more, preferably 95% or more.
- the number average degree of polymerization is usually 50 or more and 5000 or less.
- Polyvinyl alcohol can also be obtained by performing a saponification reaction of a vinyl carboxylate polymer in a polycondensation reaction of a metal alkoxide and / or its hydrolysis condensate (C) described later.
- examples of the vinyl carboxylate polymer which is a starting material include polyvinyl acetate and vinyl polypropionate.
- a copolymer with another monomer can also be used. Examples include an ethylene-vinyl acetate copolymer and an ethylene-vinyl propionate copolymer.
- the water-soluble polymer (B) having a carboxyl group in the present invention is a water-soluble polymer containing at least two carboxyl groups in the polymer chain.
- the water-soluble polymer (B) having a carboxyl group is preferably poly (meth) acrylic acid or a partially neutralized product thereof, more preferably at least two acrylic acid or methacrylic acid units in the molecule.
- polyacrylic acid or polymethacrylic acid polyacrylic acid or polymethacrylic acid
- copolymer containing another monomer unit may be sufficient. These may be used alone or in combination of two or more.
- poly (meth) acrylic acid or acrylic acid / methacrylic acid copolymer which is a single polymer is, for example, acrylic acid or Obtained by radical (co) polymerization of methacrylic acid.
- Copolymers with other monomers include (meth) acrylic acid and olefins having 2 to 30 carbon atoms such as ethylene, propylene and 1-butene, such as acrylic acid, methacrylic acid, crotonic acid and maleic acid.
- Aliphatic or aromatic esters, salts, anhydrides and amides derived from unsaturated carboxylic acids having 3 to 30 carbon atoms such as fumaric acid, such as acrylonitrile and methacrylonitrile having 3 to 30 carbon atoms It can be obtained by copolymerization with unsaturated nitriles such as vinyl ethers having 3 to 30 carbon atoms such as methyl vinyl ether and ethyl vinyl ether.
- poly (meth) acrylic acid may be obtained by neutralizing all or part of carboxyl groups (carboxylic acid groups) with alkali or alkaline earth metal hydroxide, ammonium hydroxide, organic ammonium hydroxide or the like. .
- the number average molecular weight of the water-soluble polymer (B) having these carboxyl groups is usually in the range of 2000 or more and 200000 or less.
- poly (meth) acrylic acid or a partially neutralized product thereof is preferred, and polyacrylic acid or a partially neutralized product thereof is particularly preferred.
- the water-soluble polymer (AB) having a hydroxyl group and a carboxyl group used in the present invention includes at least one hydroxyl group in the polymer chain, and It is a water-soluble polymer containing at least one carboxyl group in its polymer chain.
- the water-soluble polymer (AB) includes, for example, vinyl esters such as vinyl formate, vinyl acetate and vinyl propionate, and, for example, 3 to 30 carbon atoms such as acrylic acid, methacrylic acid, crotonic acid, maleic acid and fumaric acid.
- the unsaturated carboxylic acids and copolymers thereof with esters, salts, anhydrides and amides thereof can be obtained by a method such as complete or partial saponification.
- the metal alkoxide in the present invention refers to one represented by the following formula (1).
- the substituent represented by R 1 is a hydrogen atom, an alkyl group (for example, methyl group, ethyl group, propyl group, etc.), an aryl group (for example, phenyl group, tolyl group, etc.), a carbon-carbon double bond-containing organic group. (e.g. acryloyl group, methacryloyl group, vinyl group), a halogen-containing group (e.g.
- R 1 existing in plural numbers may be the same or different .
- R 2 represents a lower alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and a plurality of OR 2 may be the same or different.
- M constituting the component (C) is a metal, and specifically, silicon, aluminum, zirconium, titanium and the like are exemplified, and these may be used in combination. Among these, silicon compounds are relatively inexpensive and easy to obtain, and the reaction proceeds slowly, so that the industrial utility value is high.
- the component (C) may be a compound that becomes a metal oxide through a sol-gel reaction by adding water and a catalyst.
- TMOS tetramethoxysilane
- TEOS tetraethoxysilane
- tetrapropoxysilane tetraisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, Methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxy Silane, diphenyldiethoxysilane, vinyltrimeth
- the component (C) is an alkoxysilane in which M is silicon (Si) in the above formula (1), alkoxyzirconium in which M is zirconium (Zr), alkoxyaluminum in which M is aluminum (Al), and M is titanium. There may be one or more selected from the group consisting of alkoxy titanium which is (Ti). Since the scratch resistance of the coating film (coating film, hard coat) is reflected in the number of alkoxy groups, it is preferable to use a tetrafunctional metal alkoxide such as tetramethoxysilane or tetraethoxysilane. Moreover, you may use these metal alkoxide and the hydrolysis polycondensate of metal alkoxide individually or in mixture of 2 or more types.
- a hydrolyzed condensate of metal alkoxide is a compound obtained by polycondensation of one or more metal alkoxides using an acid or alkali compound as a catalyst.
- partial hydrolysis polycondensation of metal alkoxides A compound include one or more selected from the group consisting of a condensate of alkoxysilane, a condensate of alkoxyzirconium, a condensate of alkoxyaluminum, and a condensate of alkoxytitanium.
- the gas barrier composition of the present invention may contain the following component (D) in addition to the water-soluble polymer (X), the component (C) and the component (E) described below.
- (D) A compound having at least one functional group capable of forming a bond with a metal oxide and one or more functional groups capable of forming a bond with a carboxyl group in one molecule.
- the compound (D) having at least one functional group capable of forming a bond and one or more functional groups capable of forming a bond with a carboxyl group is a water-soluble polymer (X) that is an organic material and an inorganic material (C). It is added in order to improve the material dispersibility with the components, and the use thereof makes it possible to obtain a coating film with higher transparency.
- a functional group capable of forming a bond with the metal oxide is a functional group that can form a bond such as a covalent bond, a hydrogen bond, or an ionic bond with a metal oxide.
- the functional group capable of forming a covalent bond with the metal oxide include an alkoxysilyl group and a silanol group
- examples of the functional group capable of forming a hydrogen bond include a hydroxyl group, a carboxyl group, and an amino group.
- an ammonium group etc. are mentioned, for example.
- a functional group capable of forming a bond with a carboxyl group Specifically, it is a functional group that can form a bond such as a covalent bond, hydrogen bond, or ionic bond with a carboxyl group.
- the functional group that can form a bond with a carboxyl group include an amino group, an epoxy group, and a thiol group.
- the functional group that can form a hydrogen bond include a monovalent group such as a hydroxyl group and a urethane bonding group. And divalent groups such as urea-binding groups.
- a functional group which can form an ionic bond an ammonium group etc. are mentioned, for example.
- the functional group capable of forming a bond with a metal oxide and the functional group capable of forming a bond with a carboxyl group in one molecule may be the same group.
- the component (D) Have more than one.
- the component (D) may have a plurality of ammonium groups.
- Examples of the compound (D) having at least one functional group capable of forming a bond with a metal oxide and one functional group capable of forming a bond with a carboxyl group in one molecule include 3-aminopropyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl)- 3-aminopropyltrimethoxysilane, 2-aminoethylaminomethyltrimethoxysilane, 3-aminopropyldimethylethoxysilane, 2- (2-aminoethylthioethyl) triethoxysilane, p-aminophenyltrimethoxysilane, N- Phenyl-3
- the functional group capable of forming a bond with the metal oxide is an alkoxysilyl group
- the functional group capable of forming a bond with the carboxyl group of the component (B) or the carboxyl group of the component (AB) is an amino group.
- the component (D) is more preferably at least one of 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane among the compounds exemplified above.
- the esterification catalyst (E) in the present invention is a compound that catalyzes a reaction of synthesizing an ester from an acid and an alcohol.
- the acid is an organic acid or an inorganic acid.
- Such a compound can be used as the esterification catalyst (E) of the present invention, but preferably a metal salt of an inorganic acid, a metal salt of an organic acid, an organic phosphorus compound, a carboxylic acid and its derivative, a sulfonic acid and Examples thereof include organic ammonium salts or pyridinium salts of mineral acids, cyano group-containing organic compounds, isocyano group-containing organic compounds, ketene derivatives, dichalcogenide compounds, cyanuric chloride, carbonyldiimidazole, and hexachloroacetone.
- an organic esterification catalyst containing an organic group that catalyzes the esterification reaction is more preferable.
- the organic esterification catalyst include organic phosphorus compounds, carboxylic acids and derivatives thereof, sulfonic acids and derivatives thereof, organic ammonium salts or pyridinium salts of mineral acids, cyano group-containing organic compounds, isocyano group-containing organic compounds, ketene derivatives, Examples include dichalcogenide compounds, cyanuric chloride, carbonyldiimidazole, and hexachloroacetone.
- inorganic acid metal salt in the present invention examples include monopotassium phosphate, dipotassium phosphate, tripotassium phosphate, potassium pyrophosphate, potassium polyphosphate, potassium metaphosphate, monosodium phosphate, and disodium phosphate.
- organic acid metal salt in the present invention examples include sodium acetate and sodium benzoate.
- the organophosphorus compound of the present invention is a phosphorous compound containing trivalent and pentavalent organic groups, and more specifically, for example, monobutyl phosphate, dioctyl phosphate, dibutyl phosphate, trioctyl phosphate, phosphoric acid.
- Phosphoric acid monoester, diester or triester having 1 to 50 carbon atoms such as triphenyl and octyl diphenyl phosphate, such as monophenyl phosphite, dibutyl phosphite, tributyl phosphite, trioctyl phosphite , Phosphite monoester, diester or triester having 1 to 50 carbon atoms such as triphenyl phosphite, and having 1 or more carbon atoms such as tributylphosphine, triphenylphosphine, tris (sulfonate phenyl) phosphine 50 or less aliphatic or aromatic phosphines, and Examples thereof include aliphatic or aromatic phosphine oxides having 1 to 50 carbon atoms such as tributylphosphine oxide and triphenylphosphine oxide, such as diphenyl chlorophosphate, triphen
- carboxylic acid and derivatives thereof of the present invention include carboxylic acid, carboxylic acid amide, carboxylic acid imide, carboxylic acid ammonium salt, carboxylic acid pyridinium salt, and carboxylic acid halide.
- the carboxylic acid may be any compound as long as it is an organic compound having a carboxyl group (—COOH group). More specifically, aliphatic or aromatic carboxylic acids having 1 to 30 carbon atoms such as formic acid, acetic acid, propionic acid, caproic acid, lauric acid, benzoic acid, o-toluic acid, such as maleic acid, adipine 2 or more and 30 or less aliphatic or aromatic dicarboxylic acids such as acid, phthalic acid, and isophthalic acid, for example, chloroacetic acid, trichloroacetic acid, 2-bromopropionic acid, o-chlorobenzoic acid and the like having 1 or more carbon atoms, 30 or less halogenated aliphatic or aromatic carboxylic acids are exemplified. Furthermore, other functional groups such as a nitro group, an alkoxy group, and a hydroxy group may be bonded to these carboxylic acids.
- Carboxylic acid amide is an amide group (-CONR 3 R 4 group, R 3 and R 4 are H or an aliphatic or aromatic hydrocarbon group having 1 to 30 carbon atoms, which may be the same or different) Specific examples include those obtained by converting the carboxyl groups of the carboxylic acids listed above into amide groups.
- the carboxylic acid imide is an organic compound having an imide group ((—CO) 2 NR group, R is H or an aliphatic or aromatic hydrocarbon group having 1 to 30 carbon atoms), and the carboxylic acids listed above Specific examples include those obtained by converting the carboxyl group of the above to an imide group.
- Carboxylic acid ammonium salts are NH 4 + or primary, secondary, tertiary or quaternary ammonium salts of carboxylic acids, and specific examples are those in which the acidic protons of the carboxylic acids listed above are replaced with these ammonium cations. Can be mentioned.
- a carboxylic acid pyridinium salt is a pyridinium salt of a carboxylic acid, and specific examples include those obtained by replacing the acidic protons of the carboxylic acids listed above with pyridinium cations.
- Carboxylic acid halide is an organic compound having an acid halide group (—COX group, X is F, Cl, Br or I), and is obtained by converting the carboxyl group of the carboxylic acid listed above into an acid halide group. Is given as a specific example.
- sulfonic acid and derivatives thereof of the present invention include sulfonic acid, sulfonamide, sulfonimide, sulfonic acid ammonium salt, sulfonic acid pyridinium salt, sulfonimide ammonium salt, sulfonimide pyridinium salt, and sulfonic acid halide. Can be mentioned.
- the sulfonic acid may be any compound as long as it is an organic compound having a sulfone group (—SO 3 H group). More specifically, aliphatic or aromatic sulfonic acids having 1 to 30 carbon atoms such as methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, such as chloromethanesulfonic acid, trifluoro Examples thereof include halogenated aliphatic or aromatic sulfonic acids having 1 to 30 carbon atoms such as methanesulfonic acid and chlorobenzenesulfonic acid. Furthermore, some of the hydrogen atoms of these sulfonic acids may be substituted with other substituents such as a nitro group, an alkoxy group, and a hydroxy group.
- the sulfonamide is an amide compound corresponding to the sulfonic acid listed above, and more specifically, for example, p-toluenesulfonic acid amide, mesitylenesulfonic acid anilide, trifluoromethanesulfonic acid-N, N-dimethyl.
- Sulfonamide compounds derived from sulfonic acid such as amide and ammonia or primary or secondary aliphatic or aromatic amine having 1 to 50 carbon atoms, such as p-toluenesulfonic acid imidazolide, mesitylenesulfonic acid imidazolide , Triisopropylbenzenesulfonic acid imidazolide, p-toluenesulfonic acid triazolide, p-toluenesulfonic acid tetrazolide, ethanesulfonic acid imidazolide, etc., or an alkylsulfonylazole having 1 to 50 carbon atoms or having 1 to 50 carbon atoms.
- sulfonic acid such as amide and ammonia or primary or secondary aliphatic or aromatic amine having 1 to 50 carbon atoms
- p-toluenesulfonic acid imidazolide mesitylenesulfonic acid imi
- Sulfonimide is an imide compound corresponding to the sulfonic acids listed above, and more specifically, includes trifluoromethanesulfonimide, p-toluenesulfonimide, chloromethanesulfonimide, and the like.
- the sulfonic acid ammonium salt is an ammonium salt corresponding to the sulfonic acid listed above.
- the ammonium cation may be NH 4 + , or a primary, secondary, tertiary or quaternary organic ammonium cation. More specifically, examples include tributylammonium triflate (tributylammonium trifluoromethanesulfonate), dimethylphenylammonium triflate, diphenylammonium triflate, triphenylammonium triflate, ammonium p-toluenesulfonate, and ammonium trichloroacetate.
- tributylammonium triflate tributylammonium trifluoromethanesulfonate
- dimethylphenylammonium triflate diphenylammonium triflate
- triphenylammonium triflate ammonium p-toluenesulfonate
- the sulfonic acid pyridinium salt is a pyridinium salt corresponding to the sulfonic acid listed above, and more specifically, for example, pyridinium-p-toluenesulfonic acid, pyridinium trifluoromethanesulfonic acid, methylpyridinium methanesulfonic acid, And butylpyridinium propionic acid.
- the sulfonimide ammonium salt is an ammonium salt corresponding to the sulfonimide listed above.
- the ammonium cation may be NH 4 + , or a primary, secondary, tertiary or quaternary organic ammonium cation. More specifically, for example, diphenylammonium trifluoromethanesulfonimide and the like can be mentioned.
- the sulfonimide pyridinium salt is a pyridinium salt corresponding to the sulfonimide listed above, and more specifically, for example, pyridinium trifluoromethanesulfonimide.
- the sulfonic acid halide is an acid halide corresponding to the sulfonic acid listed above, and more specifically, for example, p-toluenesulfonic acid chloride, mesitylenesulfonic acid chloride, triisopropylbenzenesulfonic acid chloride. And trifluoromethanesulfonic acid bromide.
- the organic ammonium salt or pyridinium salt of a mineral acid of the present invention is a salt of a mineral acid whose cation is a primary, secondary, tertiary or quaternary organic ammonium cation or pyridinium cation.
- Examples include diphenylammonium, tetraethylammonium chloride, and pyridinium sulfate.
- the cyano group-containing organic compound of the present invention is an organic compound in which a cyano group (—CN group) is bonded to a carbon, nitrogen, oxygen or sulfur atom.
- the organic compound may have a functional group other than a cyano group in the molecule.
- aliphatic or aromatic nitrile compounds having 1 to 30 carbon atoms such as propionitrile, malononitrile, and benzonitrile; Halogenated aliphatic or aromatic nitrile compounds having 1 to 30 carbon atoms such as trichloroacetonitrile and bromoacetonitrile p-chlorobenzonitrile; Nitrogen-containing aliphatic or aromatic nitrile compounds having 1 to 30 carbon atoms such as cyanopyridine and tris (2-cyanoethyl) nitromethane; Sulfur-containing aliphatic or aromatic nitrile compounds having 1 to 30 carbon atoms such as cyanomethylbenzenesulfonate; Aliphatic or aromatic having 1 to 50 carbon atoms such as dicyanodiamide, 1-cyanoisourea, N-cyanoformamide, N-cyanoacetamide, 1-cyanobenzotriazole, 1-pyrrolidinecarbonitrile, 4-morpholinecarbonitrile Group
- the isocyano group-containing organic compound of the present invention is an organic compound in which an isocyano group (—NC group) is bonded to a carbon, nitrogen, oxygen or sulfur atom.
- the organic compound may have a functional group other than the isocyano group in addition to the isocyano group.
- aliphatic or aromatic isocyano compounds having 1 to 30 carbon atoms such as cyclohexyl isocyanate, isopropyl isocyanide, 2,6-dimethylphenyl isocyanide; 2-morpholinoethyl isocyanide, diethylisocyanomethylphospho And heteroatom-containing aliphatic or aromatic isocyano compounds having 1 to 30 carbon atoms such as narate and ethyl isocyanoacetate.
- the ketene derivative of the present invention is an organic compound in which ketene is generated by, for example, ketene and thermal decomposition. Specifically, ketene, diketene, ketene diethyl acetal, 1,1-bis (methylthio) ethylene, 2,2, Examples include 6-trimethyl-4H-1,3-dioxin-4-one.
- the dichalcogenide compound of the present invention is an organic compound having a disulfide group (—SS— group) or a diselenide (—SeSe— group), and more specifically, for example, 2,2′-dipyridyl disulfide, 2,2 And '-dipyridyl diselenide.
- organic esterification catalysts sulfonic acid and its derivatives and cyano group-containing organic compounds are preferred.
- examples of specific combinations of the compounds exemplified above include the following.
- component one or more compounds selected from the group consisting of polyvinyl alcohol, ethylene-vinyl alcohol copolymer, and saccharide
- component poly (meth) acrylic acid or a partially neutralized product thereof
- component (C) One or more selected from the group consisting of alkoxysilane, alkoxyzirconium, alkoxyaluminum and alkoxytitanium and / or its hydrolysis condensate
- component esterification catalyst
- component polyvinyl alcohol
- component polyacrylic acid
- C component: tetramethoxysilane
- E component: dicyanodiamide
- component (D) specific combinations in the case of further including component (D) include the following.
- component polyvinyl alcohol
- component polyacrylic acid
- C component: tetramethoxysilane
- D component: 3-aminopropyltrimethoxysilane or 3-aminopropyltriethoxysilane
- E component: dicyanodiamide
- the gas barrier composition according to the present invention includes "(i) a mixture of a water-soluble polymer having a hydroxyl group (A) and a water-soluble polymer having a carboxyl group (B)", and "(ii ) Water-soluble polymer (X) containing at least one of water-soluble polymer (AB) having hydroxyl group and carboxyl group], metal alkoxide and / or metal alkoxide hydrolysis condensate (C), and esterification catalyst (E) is an essential component.
- a water-soluble polymer having a hydroxyl group (A) and a water-soluble polymer having a carboxyl group (B) includes "(ii) a mixture of a water-soluble polymer having a hydroxyl group (A) and a water-soluble polymer having a carboxyl group (B)", and “(ii ) Water-soluble polymer (X) containing at least one of water-soluble polymer (AB) having hydroxyl group and carboxyl group], metal
- the amount of the metal alkoxide and / or its hydrolysis condensate (C) used in the present invention is 460 parts by weight or more and 2700 parts by weight or less with respect to 100 parts by weight of the water-soluble polymer (X).
- a higher gas barrier property is exhibited than a coating film consisting of only a water-soluble polymer.
- the film obtained from the gas barrier composition can suppress deterioration of the gas barrier property under high temperature and high humidity conditions, and can maintain high gas barrier ability.
- it is preferably 460 parts by weight or more and 1600 parts by weight or less. More preferably, it is 460 to 1500 parts by weight, and particularly preferably 460 to 1400 parts by weight.
- the esterification catalyst (E) used in the present invention is 0.01 parts by weight or more and 100 parts by weight or less, preferably 0.1 parts by weight or more, with respect to 100 parts by weight of the water-soluble polymer (X). 60 parts by weight or less.
- esterification catalysts (E) water resistance is inadequate, and when too much, transparency of a coating film will fall. If it is in the said range, the deterioration of the gas barrier property in high temperature and a high humidity condition will be suppressed, and the hard coat excellent in transparency can be obtained.
- the gas barrier composition of the present invention may further contain the above component (D).
- the amount of the compound (D) used in the present invention having at least one functional group capable of forming a bond with a metal oxide in one molecule and one or more functional groups capable of forming a bond with a carboxyl group, For example, 0.1 part by weight or more and 20 parts by weight or less, preferably 1 part by weight or more and 20 parts by weight or less, more preferably 1 part by weight or more and 15 parts by weight with respect to 100 parts by weight of the water-soluble polymer (X). Part or less, more preferably 1 part by weight or more and 10 parts by weight or less.
- the gas barrier composition in the present invention includes a water-soluble polymer having a hydroxyl group (A), a water-soluble polymer having a carboxyl group (B), a metal alkoxide and / or a hydrolysis condensate of metal alkoxide (C), It is preferable that the esterification catalyst (E) is an essential component.
- A water-soluble polymer having a hydroxyl group
- B water-soluble polymer having a carboxyl group
- C metal alkoxide and / or a hydrolysis condensate of metal alkoxide
- E is an essential component.
- the weight ratio of the water-soluble polymer (A) having a hydroxyl group and the water-soluble polymer (B) having a carboxyl group is 97/3 to 3/97, and 95/5 to 5 in terms of further improving the water resistance. / 95 is preferred, more preferably 90/10 to 10/90.
- the water resistance of the coating film is ( The optimum value is set in consideration of the ratio with the components C) and (D).
- the gas barrier property of the resulting coating film can be further improved as compared with the case of blending a large amount of the component (B).
- the adhesion of the coating film to the material to be coated depends on the material to be coated, but depending on the material to be coated, the component (A) The adhesion of the resulting coating film to the material to be coated can be further improved as compared with the case where a large amount is blended.
- the amount of the metal alkoxide and / or its hydrolysis condensate (C) used in the present invention is 460 parts by weight or more and 1600 parts by weight or less based on 100 parts by weight of the mixture of the component (A) and the component (B). It is.
- the gas barrier property is higher than that of the coating film composed only of the components (A) and (B).
- the film obtained from the gas barrier composition can suppress deterioration of the gas barrier property under high temperature and high humidity conditions, and can maintain high gas barrier ability.
- it is preferably 460 parts by weight or more and 1500 parts by weight or less. More preferably, it is 460 parts by weight or more and 1400 parts by weight or less.
- the esterification catalyst (E) used in the present invention is 0.01 parts by weight or more and 100 parts by weight or less with respect to 100 parts by weight of the mixture of the components (A) and (B). 1 to 60 parts by weight.
- esterification catalysts (E) water resistance is inadequate, and when too much, transparency of a coating film will fall. If it is in the said range, the deterioration of the gas barrier property in high temperature and a high humidity condition will be suppressed, and the hard coat excellent in transparency can be obtained.
- the gas barrier composition of the present invention may further contain the above component (D).
- the amount of the compound (D) used in the present invention having at least one functional group capable of forming a bond with a metal oxide in one molecule and one or more functional groups capable of forming a bond with a carboxyl group, For example, 0.1 part by weight or more and 20 parts by weight or less, preferably 1 part by weight or more and 20 parts by weight or less, and more preferably 1 part by weight with respect to 100 parts by weight of the mixture of component (A) and component (B)
- the amount is 15 parts by weight or less, and more preferably 1 part by weight or more and 10 parts by weight or less.
- the gas barrier composition of the present invention may further contain other components.
- the gas barrier composition of the present invention may contain what can be a catalyst for the hydrolysis / polymerization reaction as shown below for the purpose of promoting the reaction in the hydrolysis / polycondensation reaction of the metal alkoxide.
- What is used as a catalyst for the hydrolysis and polymerization reaction of metal alkoxides is “the latest functional sol-gel fabrication technology by sol-gel method” (by Hirashima Satoshi, General Technical Center, P29) and “sol-gel method This is a catalyst used in a general sol-gel reaction described in “Science” (Sakuo Sakuo, Agne Jofusha, P154).
- inorganic and organic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, tartaric acid, and toluenesulfonic acid
- alkali metal water such as ammonium hydroxide, potassium hydroxide, and sodium hydroxide Oxides, quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, ammonia, triethylamine, tributylamine, morpholine, pyridine, piperidine, ethylenediamine, diethylenetriamine, ethanolamine, diethanolamine, Amines such as triethanolamine, aminosilanes such as 3-aminopropyltriethoxysilane, and N (2-aminoethyl) -3-aminopropyl
- organotin compounds titanium tetraisopropoxide, diisopropoxytitanium bisacetylacetonate, zirconium tetrabutoxide, zirconium tetrakisacetylacetonate, aluminum triisopropoxide, aluminum trisethylacetonate, trimethoxyborane, etc.
- a metal alkoxide etc. can be used. From the standpoint of reactivity, it is preferable to use an acid catalyst such as hydrochloric acid or nitric acid, where the reaction proceeds relatively gently.
- the amount of the catalyst used is preferably 0.001 mol or more and 0.05 mol or less, preferably 0.001 mol or more and 0.04 mol or less, more preferably 0.001 mol or more, based on 1 mol of the metal alkoxide. 0.03 mol or less.
- water may be added to the metal alkoxide and / or its hydrolysis condensate (C) for the purpose of hydrolyzing the metal alkoxide and / or its hydrolysis condensate (C).
- the amount of water to be added is 10 molar equivalents or less, preferably 4 molar equivalents or less, more preferably 3 molar equivalents, based on the total alkoxy groups contained in the metal alkoxide and / or its partially hydrolyzed polycondensate. It is as follows.
- the preferred reaction temperature during the hydrolytic polycondensation of the metal alkoxide is 1 ° C. or more and 100 ° C. or less, more preferably 20 ° C. or more and 60 ° C. or less, and the reaction time is 1 hour or more and 50 hours. The following degrees are preferred.
- the gas barrier composition of the present invention may further contain metal oxide fine particles. By adding metal oxide fine particles, the scratch resistance of the hard coat is improved.
- the metal oxide fine particles refer to oxide fine particles composed of at least one element selected from silicon, aluminum, titanium, zirconium, indium, tin, zinc, and antimony.
- the metal oxide fine particles preferably have an average particle diameter in the BET method of 1 nm or more from the viewpoint of further improving scratch resistance and 100 nm or less from the viewpoint of further improving transparency. Specific examples of the metal oxide fine particles include the following.
- the silica fine particles are manufactured by Nissan Chemical Industries, Ltd. Trade names: Methanol Silica Sol, MA-ST-MA, MEK-ST, MIBK-ST, IPA-ST, IPA-ST-UP, IPA-ST-MS, IPA- ST-L, IPA-ST-ZL, NPC-ST-30, NBA-ST, XBA-ST, EG-ST, DMAC-ST, ST-20, ST-30, ST-40, ST-C, ST- N, ST-O, ST-S, ST-50, ST-20L, ST-OL, ST-XS, ST-XL, ST-YL, ST-ZL, QAS-40, LSS-35, LSS-45, ST-UP, ST-OUP, ST-AK, manufactured by Nippon Aerosil Co., Ltd.
- alumina fine particles trade names: Alumina Sol-100, Alumina Sol-200, Alumina Sol-520, etc. manufactured by Nissan Chemical Industries, Ltd. can be exemplified.
- Examples of alumina powder, titanium oxide powder, indium oxide powder, tin oxide powder, and zinc oxide powder dispersion product are manufactured by CI Kasei Co., Ltd. and trade name: Nanotech.
- metal oxide fine particles are contained in an amount of 1 to 100 parts by weight, preferably 1 to 60 parts by weight, based on 100 parts by weight of the gas barrier composition.
- fine-particles the transparency of a coating film will fall, and when too few, the effect by addition is inadequate. If it is in the said range, the hard coat which was further excellent in the balance of transparency, water resistance, gas barrier property, and abrasion resistance can be obtained.
- Gas barrier composition of the present invention may further contain a solvent. Including a solvent is preferable because it facilitates the step of applying a coating material comprising a gas barrier composition to the resin surface.
- the solvent that can be used may be either an aqueous solvent or an organic solvent, and is not particularly limited as long as it dissolves or disperses the gas barrier composition of the present invention.
- Alcohols having 1 to 30 carbon atoms such as methanol, ethanol and propanol; aliphatic or aromatic hydrocarbons having 4 to 30 carbon atoms, such as n-hexane, n-heptane, toluene, xylene; Halogen-containing aliphatic or aromatic hydrocarbons having 1 to 30 carbon atoms such as dichloromethane, chloroform, chlorobenzene, o-dibromobenzene; Aliphatic or aromatic ethers having 2 to 30 carbon atoms, such as diethyl ether and diphenyl ether; Aliphatic or aromatic esters having 2 to 30 carbon atoms, such as ethyl acetate and butyl propionate; Aliphatic or aromatic amide compounds having 2 to 30 carbon atoms such as dimethylformamide and dimethylacetamide; And aliphatic or aromatic nitriles having 2 to 30 carbon atoms such as acetonitrile and benzon
- water or a mixed solvent of water and alcohol is particularly preferable.
- the alcohol methanol, ethanol, propanol, isopropanol and the like are preferable.
- the mixing ratio of water and alcohol is preferably 2/8 to 8/2 by weight.
- the amount of the solvent to be used is not particularly limited, but with respect to 100 parts by weight of the water-soluble polymer (preferably a mixture of the water-soluble polymer (A) having a hydroxyl group and the water-soluble polymer (B) having a carboxyl group). Usually, it is in the range of 1 to 1,000,000 parts by weight, more preferably in the range of 10 to 10,000 parts by weight.
- the gas barrier composition in the present invention includes “(i) a water-soluble polymer having a hydroxyl group (A) and a water-soluble polymer having a carboxyl group (B)” and “(ii) a water-soluble polymer having a hydroxyl group and a carboxyl group.
- the gas barrier composition in the present invention includes, for example, a solution obtained by dissolving the above water-soluble polymer (X) in any of the above solvents, a metal alkoxide and / or a metal alkoxide hydrolysis condensate (C), It is prepared by mixing with an esterification catalyst (E).
- the mixing order of the water-soluble polymer (X) and the component (C) is not particularly limited, and can be mixed in an arbitrary order.
- the component (C) may be added to the mixture of the component (A) and the component (B), the component (B) may be added to the mixture of the component (A) and the component (C), The component (A) may be added to the mixed solution of the component (C) and the component (C).
- the catalyst in which component (C) is hydrolyzed and polycondensed to solidify the sol as a gel and an oxide solid is formed by heating the gel, the catalyst is previously washed with water. It may be added after dissolving or diluting.
- the gas barrier composition of the present invention further comprises a compound (D) having at least one functional group capable of forming a bond with a metal oxide and one functional group capable of forming a bond with a carboxyl group in one molecule. May be.
- (D) component is added so that it may become the quantity of 0.1 to 20 weight part with respect to 100 weight part of water-soluble polymer (X).
- the component (D) can be added at any point in the above production method in relation to the water-soluble polymer (X) and the component (C).
- ester catalyst (E) may be added at any time, for example, in the presence of a solution of the water-soluble polymer (X).
- the method for producing the gas barrier composition of the present invention is not particularly limited.
- the following methods (a) to (h) are preferable, and (a) to (d) are more preferable.
- the following is an example in the case of manufacturing the gas-barrier composition containing (D) component.
- (A) a step of mixing the water-soluble polymer (X), the component (D) and the component (E) in a solvent, and a step of mixing the liquid mixture obtained in the previous step and the component (C), A method of proceeding a hydrolysis condensation reaction of the component (C) in the step of mixing the mixed solution and the component (C).
- step (D) a step of mixing the component (X), and a step of mixing the liquid mixture obtained in the previous step, the component (D), the component (E) and the component (C), In the step of mixing the mixed solution, the component (D), the component (E) and the component (C), the hydrolysis condensation reaction of the component (C), and the component (D), at least one of the metal oxide and the carboxyl group, To advance the reaction.
- (H) A solution in which a catalyst and water are added to the step of mixing the component (X) and the mixed solution obtained in the previous step, the component (D), the component (E), and the component (C), and stirred for a predetermined time.
- a catalyst and water are added to the step of mixing the component (X) and the mixed solution obtained in the previous step, the component (D), the component (E), and the component (C), and stirred for a predetermined time.
- the hydrolysis condensation reaction of the component (C) is further advanced.
- (D) a method of allowing the component to react with at least one of a metal oxide and a carboxyl group.
- the component (D) reacts with both the metal oxide and the carboxyl group in the reaction between the component (D) and at least one of the metal oxide and the carboxyl group.
- the reaction of component (D) is specifically a binding reaction with at least one of a metal oxide and a carboxyl group, and component (D) is bonded to both the metal oxide and the carboxyl group. Is preferred.
- the gas barrier composition in the present invention comprises a water-soluble polymer having a hydroxyl group (A), a water-soluble polymer having a carboxyl group (B), a metal alkoxide and / or a hydrolysis condensate thereof (C), and an esterification catalyst ( It can be obtained by mixing E).
- the manufacturing method of the gas-barrier composition in this invention mix
- the gas barrier composition in the present invention includes, for example, a solution in which a water-soluble polymer (A) having a hydroxyl group and a water-soluble polymer (B) having a carboxyl group are dissolved in any of the above solvents, a metal alkoxide, and / or Alternatively, it is prepared by mixing a hydrolysis condensate (C) of a metal alkoxide and an esterification catalyst (E).
- the mixing order of the component (A), the component (B), and the component (C) is not particularly limited, and can be mixed in any order.
- the component (C) may be added to the mixture of the component (A) and the component (B), the component (B) may be added to the mixture of the component (A) and the component (C), The component (A) may be added to the mixed solution of the component (C) and the component (C).
- component (C) in which component (C) is hydrolyzed and polycondensed to solidify the sol as a gel and an oxide solid is formed by heating the gel, the catalyst is previously washed with water. It may be added after dissolving or diluting.
- Component (C) can be added by reacting component (C) alone and then adding to component (A) or component (B) or a mixture thereof, or component (C) as component (A). After mixing and reacting with (B) component, or mixing (C) component with (B) component and reacting, (A) component and the like can be mentioned. .
- the gas barrier composition of the present invention further comprises a compound (D) having at least one functional group capable of forming a bond with a metal oxide and one functional group capable of forming a bond with a carboxyl group in one molecule. May be.
- (D) component is added so that it may become the quantity of 0.1 to 20 weight part with respect to 100 weight part of mixture of (A) component and (B) component.
- the component (D) can be added at any point in the above production method in relation to the components (A) to (C), but the functional group capable of forming a bond with the metal oxide is an alkoxy group.
- the following method (1) or (2) can be exemplified. In the present invention, any method may be used.
- a metal oxide and a bond can be formed in one molecule in a solution obtained by dissolving a water-soluble polymer (A) having a hydroxyl group and a water-soluble polymer (B) having a carboxyl group in any of the above solvents.
- a solution in which a compound (D) having at least one functional group and one or more functional groups capable of forming a bond with a carboxyl group is dropped and mixed, and a metal alkoxide and / or a hydrolysis condensate of metal alkoxide (C) Alternatively, a method in which a solution obtained by adding a catalyst and water to the component (C) and stirring for a predetermined time is mixed immediately before use and then reacted at a predetermined temperature for a predetermined time.
- ester catalyst (E) may be added at any time, for example, in the presence of a solution of the component (A) or the component (B).
- the method for producing the gas barrier composition of the present invention is not particularly limited.
- the following methods (i) to (viii) are preferable, and (i) to (iv) are more preferable.
- the following is an example in the case of manufacturing the gas-barrier composition containing (D) component.
- (I) a step of mixing the component (A), the component (B), the component (D) and the component (E) in a solvent, and a step of mixing the liquid mixture obtained in the previous step and the component (C).
- (Vi) A step of mixing the component (A), the component (B) and the component (E) in a solvent, and the mixed solution obtained in the previous step, the component (D), and the component (C) with catalyst and water. Adding and mixing the stirred solution for a certain period of time, In the step of adding a catalyst and water to the mixed solution, the component (D), and the component (C) and mixing the solution stirred for a predetermined time, the hydrolysis condensation reaction of the component (C) is further advanced, and (D) A method of causing a reaction between a component and at least one of a metal oxide and a carboxyl group.
- the component (D) in the reaction of the component (D) with at least one of the metal oxide and the carboxyl group, is a metal oxide and a carboxyl group. It is preferred to react with both.
- the reaction of component (D) is specifically a binding reaction with at least one of a metal oxide and a carboxyl group, and component (D) is bonded to both the metal oxide and the carboxyl group. Is preferred.
- Coating film (gas barrier hard coat, gas barrier film)
- the coating film of the present invention is produced by forming a film-like product of the gas barrier composition of the present invention and heat-treating it.
- the film-like material refers to a state where the composition covers the surface of the substrate.
- the method for forming the film-like material is not particularly limited. For example, there is a method in which a solution of a gas barrier composition is cast on a support such as a glass plate, a metal plate, or a thermoplastic resin film and dried. After a film-like material is formed on the support to a desired thickness, heat treatment is performed.
- the heat treatment temperature is usually in the range of 50 ° C. or higher and 250 ° C. or lower, more preferably in the range of 80 ° C.
- esterification catalyst (E) for example, it becomes possible to develop a high gas barrier property at a lower temperature. By performing the heat treatment at a lower temperature, coloring of the coating film can be suppressed. Moreover, when using a thermoplastic resin film as a support body, it is also possible to manufacture a coating film on a low melting point resin film.
- the heat treatment time is usually 1 second or longer.
- the film thickness of the coating film of the present invention is 0.01 ⁇ m or more and 100 ⁇ m or less, preferably 0.1 ⁇ m or more and 70 ⁇ m or less. If the film thickness is too large, cracks may occur in the coating film.
- the coating film made of the gas barrier composition according to the present invention is excellent in gas barrier properties such as gas and water vapor.
- gas barrier property of the gas barrier hard coat of the present invention when a 0.7 ⁇ m thick coating film is laminated on a 50 ⁇ m thick polyimide film, the temperature is 23 ° C. and the humidity is 90%.
- the oxygen permeability (cc / m 2 ⁇ day ⁇ atm) of the laminate measured using an oxygen permeability measuring device (OXTRAN 2 / 21MH manufactured by MOCON) is 10 or less, preferably 9 or less.
- the oxygen permeability (cc / m 2 ⁇ day ⁇ atm) of the coating film measured by the same method is 23 or less, preferably 18 or less.
- the lower limit of the oxygen permeability can be set to 0.01 or more.
- the coating film made of the gas barrier composition according to the present invention is suppressed in deterioration under high temperature and high humidity conditions, and is excellent in gas barrier properties such as gas and water vapor.
- a wet heat test (standing at a temperature of 40 ° C. and a humidity of 90% for 24 hours) is performed, and when the oxygen permeability is measured again, the oxygen permeability of the laminate (cc / m 2) (Day ⁇ atm) is 11 or less, preferably 10 or less, more preferably 9 or less.
- the oxygen permeability of the coating film after the wet heat test measured by the same method is 30 or less, preferably 23 or less, more preferably 18 or less. Note that the lower limit of the oxygen permeability can be set to 0.01 or more.
- the laminate (gas barrier laminate film, hard coat laminate) of the present invention is a laminate comprising at least one coating film of the present invention. Specifically, (I) a laminate in which the coating film of the present invention is laminated on a substrate; and (ii) a laminate in which the coating film of the present invention and a plastic substrate are laminated. (Iii) a plastic substrate and the plastic substrate. A laminated body provided with a vapor deposition film made of an inorganic compound formed thereon and the coating film of the present invention formed on the vapor deposition film is exemplified.
- the substrate in the laminate (i) include an insulating substrate, a semiconductor substrate, and a metal substrate.
- the insulating substrate include a glass substrate and an organic resin substrate such as a polycarbonate substrate.
- a laminate film of the coating film of the present invention and another flexible film can be mentioned. More specifically, there may be mentioned those comprising at least two layers of the coating film of the present invention and a thermoplastic resin film.
- a resin film having thermoplasticity can be used as the plastic substrate used.
- resin films such as polyethylene, polypropylene and cycloolefin copolymers, polyamide resin films such as nylon 6 and nylon 66, polyimide resin films such as polyester resin films such as polyethylene terephthalate and polyethylene naphthalate, and the like. It is done. Or the film which consists of a mixture of these resin, or the laminated body of these films may be sufficient. These films may be unstretched films or stretched films.
- the method for obtaining the laminate of the present invention is not particularly limited, and a known lamination method such as a coating method, a dry lamination method, and an extrusion coating method can be employed.
- a laminate such as a laminated film can be obtained by coating a thermoplastic film with the coating material of the present invention to a desired thickness and performing a heat treatment.
- the method for coating the thermoplastic resin film with the coating material comprising the gas barrier composition is not particularly limited, and can be performed by a usual method.
- the coating material may be applied to the thermoplastic resin film after biaxial stretching and then subjected to heat treatment.
- the coating material may be applied to an unstretched film and subjected to simultaneous biaxial stretching and heat treatment. After the uniaxial stretching, a coating material may be applied and then stretched in the width direction and heat-treated.
- the coating film of the present invention and the thermoplastic resin film are bonded together by a known method.
- a thermoplastic resin is melt-extruded on the coating film of the present invention to obtain a laminated film.
- a laminate comprising at least three layers in which a plastic substrate, a vapor deposition film made of an inorganic compound, and the coating film of the present invention are laminated in order.
- the vapor barrier film is interposed between the plastic substrate and the coating film of the present invention, so that the gas barrier property can be further improved.
- Deposition films include AlO, SiN, SiO, diamond-like carbon (Diamond-like Carbon) or the like can be used, and these can be used in combination.
- a method for forming the deposited film a known method can be used. Vapor Deposition, Chemical Vapor Deposition) and the like.
- the coating film obtained from the gas barrier composition in the present invention is, for example, once. It is also possible to obtain physical properties equivalent to those of the laminated film by coating.
- a gas barrier hard coat composition capable of producing a resin film having transparency, gas barrier properties under high humidity, and scratch resistance at a heat treatment temperature lower than conventional, and a film form of the hard coat composition It is also possible to obtain a gas barrier hard coat obtained by heat-treating a product and a method for producing the same.
- the obtained coating film can be used for the following applications.
- Photochromic compound-containing resin coating materials Conventionally, so-called photochromic compounds that develop color or change color by absorbing light in the ultraviolet region are known.
- a photochromic compound-containing resin obtained by adding this photochromic compound to a resin is widely used. For example, it is formed into a thin film between glasses and used for glass for automobiles and window glass. Further, it is used as a photochromic lens by kneading into a spectacle lens material or by laminating on a lens.
- a photochromic lens is a lens that quickly colors with ultraviolet light contained in sunlight and functions as sunglasses outdoors and functions as normal glasses that fade and transparent indoors.
- These photochromic products have a problem in that the coloring and fading action in response to ultraviolet light irradiation does not last.
- the cause is considered to be deterioration of the photochromic compound due to contact with ultraviolet light or atmospheric oxygen and moisture.
- these products are required to have durability that can maintain the coloring and fading action even when used for a long time under high humidity.
- deterioration of gas barrier properties under high temperature and high humidity conditions is suppressed.
- the film of this invention is laminated
- a hard coat layer is laminated to prevent damage to the lens.
- the coating film of the present invention has a hard coat ability in addition to the gas barrier ability, the hard coat film is laminated. Is no longer necessary.
- glass has been used for display substrates.
- plastics with features such as thin, light, and unbreakable have been replaced in order to cope with the reduction in size and weight of displays.
- plastics have the above-mentioned characteristics, they have problems in scratch resistance such as gas barrier properties, dimensional stability, heat resistance, chemical resistance, low water absorption, optical anisotropy, and the like.
- the gas barrier property is required to have high performance in order to cause problems such as display defects due to the penetration of water vapor and oxygen into the display element.
- the gas barrier property is maintained even under high temperature and high humidity conditions, so the gas in the atmosphere is blocked for a long period of time and the display element is prevented from deteriorating. can do.
- the hard coat ability can be imparted to the substrate.
- Example 1 (Preparation of gas barrier (for hard coat) composition) Polyvinyl alcohol aqueous solution As component (A), 95 parts by weight of distilled water is added to 5 parts by weight of polyvinyl alcohol (PVA) 500 manufactured by Wako Pure Chemical Industries, Ltd., and a completely saponified type (average polymerization degree: about 400 to 600). Was dissolved under heating to obtain a 5% by weight aqueous solution of PVA.
- PVA polyvinyl alcohol
- Polyacrylic acid aqueous solution As component (B), 30 parts by weight of distilled water is added to 20 parts by weight of a polyacrylic acid (PAA) aqueous solution (25%) (viscosity: 8000 to 12000 cP (30 ° C.)) manufactured by Wako Pure Chemical Industries, Ltd. In addition, a 10% by weight aqueous solution of PAA was obtained. In the following Examples and Comparative Examples, these aqueous solutions were used as an aqueous solution containing the component (A) and an aqueous solution containing the component (B), respectively.
- PAA polyacrylic acid
- aqueous solution 25%) (viscosity: 8000 to 12000 cP (30 ° C.)) manufactured by Wako Pure Chemical Industries, Ltd.
- a 10% by weight aqueous solution of PAA was obtained.
- these aqueous solutions were used as an aqueous solution containing the component (A) and an aqueous solution containing the component (B), respectively.
- solution (1) To 771 parts by weight of methanol, 460 parts by weight of (C) component tetramethoxysilane (TMOS) and 23 parts by weight of (E) component dicyanodiamide were added, and then stirred until the dicyanodiamide was dissolved. This is designated as solution (1). After adding 700 parts by weight of PAA 10% by weight aqueous solution and 838 parts by weight of water to 600 parts by weight of PVA 5% by weight aqueous solution, stirring this aqueous solution, (A) component 3-aminopropyltrimethoxysilane (APTMOS) and ethanol was added dropwise at a weight ratio of 1: 9 and further stirred at room temperature for 30 minutes. This is designated as solution (2). The solution (1) was added to the solution (2) and stirred at 30 ° C. for 1.5 hours to obtain a gas barrier composition.
- TMOS component tetramethoxysilane
- E component dicyanodiamide was dissolved.
- solution (2) After adding 700 parts by weight of
- composition prepared by the above method is applied to a polyimide film of 50 ⁇ m thickness (manufactured by Toray DuPont Co., Ltd., Kapton 200EN film thickness of 50 ⁇ m) using a bar coater so that the thickness after curing is about 0.7 ⁇ m. It was applied to. Then, it heated at 40 degreeC for 10 minutes, and 110 degreeC for 2 hours, and obtained the coating film.
- Example 2 To 778 parts by weight of methanol, 460 parts by weight of (C) component tetramethoxysilane (TMOS) and 23 parts by weight of (E) component dicyanodiamide were added, followed by stirring until the dicyanodiamide was dissolved. This is designated as solution (3).
- TMOS tetramethoxysilane
- E component dicyanodiamide
- Example 3 To 775 parts by weight of methanol, 465 parts by weight of tetramethoxysilane (TMOS) as component (C) and 23 parts by weight of dicyanodiamide as component (E) were added, followed by stirring until the dicyanodiamide was dissolved. This is designated as solution (5). After adding 700 parts by weight of PAA 10% by weight aqueous solution and 851 parts by weight of water to 600 parts by weight of PVA 5% by weight aqueous solution, stirring this aqueous solution, (A) component 3-aminopropyltrimethoxysilane (APTMOS) and ethanol was added dropwise at a weight ratio of 1: 9 and further stirred at room temperature for 30 minutes. This is designated as solution (6). The solution (5) was added to the solution (6) and stirred at 30 ° C. for 1.5 hours to obtain a gas barrier composition. Using this, it was applied and heated in the same manner as in Example 1 to obtain a coating film.
- TMOS tetrameth
- Example 4 To 810 parts by weight of methanol, 500 parts by weight of tetramethoxysilane (TMOS) as component (C) and 23 parts by weight of dicyanodiamide as component (E) were added, followed by stirring until the dicyanodiamide was dissolved. This is designated as solution (7).
- TMOS tetramethoxysilane
- Example 5 To 824 parts by weight of methanol, 528 parts by weight of tetramethoxysilane (TMOS) as component (C) and 23 parts by weight of dicyanodiamide as component (E) were added, followed by stirring until the dicyanodiamide was dissolved. This is designated as solution (9). After adding 700 parts by weight of PAA 10% by weight aqueous solution and 1013 parts by weight of water to 600 parts by weight of PVA 5% by weight aqueous solution, while stirring this aqueous solution, (A) component 3-aminopropyltrimethoxysilane (APTMOS) and ethanol was added dropwise at a weight ratio of 1: 9 and further stirred at room temperature for 30 minutes. This is designated as solution (10). The solution (9) was added to the solution (10) and stirred at 30 ° C. for 1.5 hours to obtain a gas barrier composition. Using this, it was applied and heated in the same manner as in Example 1 to obtain a coating film.
- TMOS tetramethoxy
- Example 7 To 1146 parts by weight of methanol, 933 parts by weight of tetramethoxysilane (TMOS) as component (C) and 23 parts by weight of dicyanodiamide as component (E) were added, followed by stirring until the dicyanodiamide was dissolved. This is designated as solution (13). After adding 700 parts by weight of PAA 10% by weight aqueous solution and 2066 parts by weight of water to 600 parts by weight of PVA 5% by weight aqueous solution, 3-aminopropyltrimethoxysilane (APTMOS) as the component (D) and ethanol are added while stirring the aqueous solution. Was added dropwise at a weight ratio of 1: 9 and further stirred at room temperature for 30 minutes.
- TMOS tetramethoxysilane
- APTMOS 3-aminopropyltrimethoxysilane
- solution (14) This is designated as solution (14).
- the solution (13) was added to the solution (14), and the mixture was stirred at 30 ° C. for 1.5 hours to obtain a gas barrier composition. Using this, it was applied and heated in the same manner as in Example 1 to obtain a coating film.
- FIG. 2 shows a cross-sectional TEM image of the coating film.
- Example 8 (Production of PET / SiN laminated film) On a 125 ⁇ m thick PET (polyethylene terephthalate) film, a silicone resin coating agent (trade name: SHC900) GE Toshiba) was gravure coated to a thickness of 2 ⁇ m and heated at 120 ° C. for 15 minutes to obtain a coating film. Subsequently, a silicon nitride (SiN) film was formed on the silicone resin layer by a CVD method so as to have a film thickness of 20 nm.
- a PET / SiN laminated film is abbreviated as a PET / SiN laminated film.
- composition prepared by the above method was applied to the PET / SiN laminated film using a bar coater so that the thickness after curing was about 2 ⁇ m. Then, it heated at 40 degreeC for 10 minutes, and 110 degreeC for 2 hours, and obtained the coating film.
- Example 9 To 1052 parts by weight of methanol, 830 parts by weight of (C) component tetramethoxysilane (TMOS) and 11.4 parts by weight of (E) component dicyanodiamide were added, followed by stirring until the dicyanodiamide was dissolved. This is designated as solution (17). 300 parts by weight of PAA 10% by weight aqueous solution and 1286 parts by weight of water were added to 1400 parts by weight of PVA 5% by weight aqueous solution, and the mixture was further stirred at room temperature for 30 minutes. This is designated as solution (18). The solution (17) was added to the solution (18) and stirred at 30 ° C. for 1.5 hours to obtain a gas barrier composition. Using this, a coating film was obtained by applying and heating on the PET / SiN laminated film in the same manner as in Example 8.
- Example 10 To 1437 parts by weight of methanol, 1300 parts by weight of (C) component tetramethoxysilane (TMOS) and 23 parts by weight of (E) component dicyanodiamide were added, and then stirred until the dicyanodiamide was dissolved. This is designated as solution (19). After adding 700 parts by weight of PAA 10% by weight aqueous solution and 3018 parts by weight of water to 600 parts by weight of PVA 5% by weight aqueous solution, while stirring this aqueous solution, (A) component 3-aminopropyltrimethoxysilane (APTMOS) and ethanol was added dropwise at a weight ratio of 1: 9 and further stirred at room temperature for 30 minutes. This is designated as solution (20). The solution (19) was added to the solution (20) and stirred at 30 ° C. for 1.5 hours to obtain a gas barrier composition. Using this, it was applied and heated in the same manner as in Example 1 to obtain a coating film.
- TMOS tetramethoxys
- Example 11 1600 parts by weight of tetramethoxysilane (TMOS) as component (C) and 23 parts by weight of dicyanodiamide as component (E) were added to 1674 parts by weight of methanol, and then stirred until the dicyanodiamide was dissolved.
- solution (21) After adding 700 parts by weight of PAA 10% by weight aqueous solution and 3797 parts by weight of water to 600 parts by weight of PVA 5% by weight aqueous solution, while stirring the aqueous solution, (A) component 3-aminopropyltrimethoxysilane (APTMOS) and ethanol was added dropwise at a weight ratio of 1: 9 and further stirred at room temperature for 30 minutes. This is designated as solution (22).
- the solution (21) was added to the solution (22) and stirred at 30 ° C. for 1.5 hours to obtain a gas barrier composition. Using this, it was applied and heated in the same manner as in Example 1 to obtain a coating film.
- Example 12 While stirring 700 parts by weight of a 10% by weight aqueous solution of PAA, 52 parts by weight of a solution prepared by mixing 3-aminopropyltrimethoxysilane (D) component and ethanol in a weight ratio of 1: 9 was added dropwise, and then stirred at room temperature for 30 minutes. did. Subsequently, 600 parts by weight of a 5% by weight aqueous solution of PVA, 23 parts by weight of dicyanodiamide as the component (E), and 1013 parts by weight of water were added and further stirred for 10 minutes.
- Example 13 600 parts by weight of PVA 5% by weight aqueous solution, 23 parts by weight of dicyanodiamide as component (E) and 1013 parts by weight of water were added to 700 parts by weight of PAA 10% by weight aqueous solution and stirred for 10 minutes. This is designated as solution (23).
- solution (23) 528 parts by weight of tetramethoxysilane (C) component was mixed with 824 parts by weight of methanol and 52 parts by weight of a solution in which 3-aminopropyltrimethoxysilane (D) component and ethanol were mixed at a weight ratio of 1: 9. The mixture was added and then stirred at room temperature for 10 minutes. This is designated as solution (24).
- the solution (24) and the solution (23) were mixed, and further stirred at room temperature for 1.5 hours. Using this, it was applied and heated in the same manner as in Example 1 to obtain a coating film.
- Example 14 700 parts by weight of PAA 10% by weight aqueous solution, 600 parts by weight of PVA 5% by weight aqueous solution, and 1013 parts by weight of water were mixed. This is designated as solution (25).
- solution (25) 528 parts by weight of (C) component tetramethoxysilane and (D) component of 3-aminopropyltrimethoxysilane mixed with ethanol in a weight ratio of 1: 9 are 52 parts by weight, and (E) component
- 23 parts by weight of dicyanodiamide and 824 parts by weight of methanol were added, followed by stirring at room temperature for 30 minutes. This is designated as solution (26).
- the solution (26) and the solution (25) were mixed, and further stirred at room temperature for 1.5 hours. Using this, it was applied and heated in the same manner as in Example 1 to obtain a coating film.
- solution (28) This is designated as solution (28).
- the solution (27) was added to the solution (28) and stirred at 30 ° C. for 1.5 hours to obtain a gas barrier composition. Using this, it was applied and heated in the same manner as in Example 1 to obtain a coating film.
- FIG. 3 shows a cross-sectional TEM image of the coating film.
- Table 1 shows the composition of the components in the above Examples and Comparative Examples together with the silica (SiO 2 ) content.
- the silica content indicates the proportion of silica contained in the coating film, and was calculated by the following method.
- silica (SiO 2 ) content The silica content was calculated on the assumption that the component (C) in the above Examples and Comparative Examples reacted 100% to become SiO 2 .
- the component (C) is TMOS
- a water-soluble polymer having a hydroxyl group (A), a water-soluble polymer having a carboxyl group (B), a metal alkoxide and / or a hydrolysis condensate thereof (C), an esterification catalyst A coating film using a gas barrier composition containing E) as a main component and containing 460 parts by weight or more and 1600 parts by weight or less of component (C) with respect to 100 parts by weight of the mixture of component (A) and component (B) In Examples 1 to 14), after the wet heat test (40 ° C.-90% RH), compared with the coating film (Comparative Examples 1 to 3) using the gas barrier composition whose component (C) is 450 parts by weight or less Had low oxygen permeability, that is, high oxygen barrier properties. From this, the coating film of the present invention suppresses the deterioration of the gas barrier property even under high temperature and high humidity conditions, and therefore the gas barrier property even under use conditions such as exposure to high temperature and high humidity conditions
- Examples 8 and 9 are not shown in FIG. 1 because they use a laminated film in which a SiN film (deposition film) is formed on a PET film.
- FIG. 2 shows a cross-sectional TEM image of the coating film produced in Example 7, and FIG. 3 shows a cross-sectional TEM image of the coating film produced in Comparative Example 1.
- the black part in the figure is composed mainly of silica formed by the sol-gel reaction of component (C) (hereinafter referred to as silica phase), and the white part is component (A) and component (B).
- the composition is composed mainly of components (hereinafter referred to as polymer phase).
- both the silica phase and the polymer phase form a continuous structure.
- the polymer phase becomes dense due to water intrusion between the polymer chains under high temperature and high humidity conditions.
- oxygen passes through the membrane through the dense polymer phase and the oxygen barrier property is lowered.
- Example 7 in which the amount of component (C) used is within the above range, the continuous structure is only the silica phase, and the polymer phase is the discontinuous structure.
- the polymer phase has a discontinuous structure, the passage of oxygen is blocked, so that the deterioration of the gas barrier property under high temperature and high humidity conditions is suppressed, and it is presumed that the high barrier property is maintained.
- the present invention also includes the following aspects.
- (1-1) Water-soluble polymer (A) having a hydroxyl group, water-soluble polymer (B) having a carboxylic acid (carboxyl group), metal alkoxide and / or their hydrolysis condensate (C), in one molecule
- the esterification catalyst (E) is a metal salt of an inorganic acid, a metal salt of an organic acid, an organic phosphorus compound, a carboxylic acid and a derivative thereof, a sulfonic acid and a derivative thereof, an organic ammonium salt or a pyridinium salt of a mineral acid, Cyano group-containing organic compound, isocyano group-containing organic compound, ketene derivative, dichalcogenide compound, cyanuric chloride, carbonyldiimidazole, hexachloroacetone, 2,4,6-trinitro-1-chlorobenzene (1) -2)
- the gas barrier hard coat composition according to any one of (1-4).
- the water-soluble polymer (A) having a hydroxyl group is one or more compounds selected from polyvinyl alcohol, ethylene-vinyl alcohol copolymer, saccharides and celluloses (1-1) to (1-5) )
- the gas barrier hard coat composition according to any one of the above.
- (1-9) 1 part by weight of metal oxide fine particles having an average particle size of 100 nm or less with respect to 100 parts by weight of the gas barrier hard coat composition described in (1-1) and / or (1-3) A gas barrier hard coat composition containing 100 parts by weight or less.
- a gas barrier laminate comprising at least one gas barrier hard coat according to (1-13).
- the esterification catalyst (E) is a metal salt of an inorganic acid, a metal salt of an organic acid, an organic phosphorus compound, a carboxylic acid and a derivative thereof, a sulfonic acid and a derivative thereof, an organic ammonium salt or a pyridinium salt of a mineral acid, It is a kind of compound selected from cyano group-containing organic compounds, isocyano group-containing organic compounds, ketene derivatives, dichalcogenide compounds, cyanuric chloride, carbonyldiimidazole, hexachloroacetone, 2,4,6-trinitro-1-chlorobenzene (2 -1)
- the composition for hard coats according to any one of (2-4).
- (2-8) A method for producing a hard coat obtained by forming a film-like product of the composition for hard coat according to any one of (2-1) to (2-7) and subjecting it to a heat treatment.
- a hard coat laminate comprising at least one hard coat according to (2-9).
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Abstract
Description
たとえば、高湿度下で樹脂フィルムを包装材として用いる場合、ガスバリア性とともに耐水性(非水溶性)も考慮に入れる必要がある。PVAの耐水性を向上させ、ガスバリア性の湿度依存性を改善するために、PVAとポリ(メタ)アクリル酸をエステル化反応により架橋させる方法がいくつか提案されてきた。
および
(ii)水酸基とカルボキシル基とを有する水溶性高分子(AB)
の少なくとも一方を含む水溶性高分子(X)と、
金属アルコキシドおよび/またはその加水分解縮合物(C)と、
エステル化触媒(E)と、を含み、
前記水溶性高分子(X)100重量部に対し、前記(C)成分を460重量部以上、2700重量部以下、前記(E)成分を0.01重量部以上、100重量部以下含む、ガスバリア性組成物。
カルボキシル基を有する水溶性高分子(B)と、
金属アルコキシドおよび/またはその加水分解縮合物(C)と、
エステル化触媒(E)と、を含み、
前記(A)成分と前記(B)成分との重量比が97/3から3/97であって、
前記(A)成分と前記(B)成分との混合物100重量部に対し、前記(C)成分を460重量部以上、1600重量部以下、前記(E)成分を0.01重量部以上、100重量部以下含む、(1)に記載のガスバリア性組成物。
前記水溶性高分子(X)100重量部に対し、前記(D)成分を0.1重量部以上、20重量部以下含む(1)に記載のガスバリア性組成物。
前記(A)成分と前記(B)成分の混合物100重量部に対し、前記(D)成分を0.1重量部以上、20重量部以下含む(2)に記載のガスバリア性組成物。
金属酸化物と結合を形成できる前記官能基が、アルコキシシリル基、シラノール基、水酸基、カルボキシル基、アミノ基およびアンモニウム基からなる群から選択される一種以上の基であって、
カルボキシル基と結合を形成できる前記官能基が、アミノ基、エポキシ基、チオール基、水酸基、ウレタン結合基、尿素結合基およびアンモニウム基からなる群から選択される一種以上の基である(3)または(4)に記載のガスバリア性組成物。
(R1)xM(OR2)y (1)
(式中、Mは、珪素、アルミニウム、ジルコニウムまたはチタニウムを表す。R1は水素原子、アルキル基、アリール基、アクリロイル基、メタクリロイル基、ビニル基またはハロゲン化アルキル基を表し、複数存在するR1は同一でも異なっていてもよい。R2は炭素数1以上、6以下の低級アルキル基を表し、複数存在するOR2基は同一でも異なっていてもよい。xおよびyは、x+y=4でありかつ、xは2以下となる整数を表す。)。
前記(B)成分がポリ(メタ)アクリル酸またはその部分中和物であって、
前記(C)成分がアルコキシシラン、アルコキシジルコニウム、アルコキシアルミニウムおよびアルコキシチタンからなる群から選ばれる一種以上および/またはその加水分解縮合物である
(2)に記載のガスバリア性組成物。
前記(D)成分が、3-アミノプロピルトリメトキシシランおよび3-アミノプロピルトリエトキシシランからなる群から選択される一種以上である(15)に記載のガスバリア性組成物。
前記(B)成分がポリアクリル酸であって、
前記(C)成分がテトラメトキシシランであって、
前記(E)成分がジシアノジアミドである
(2)に記載のガスバリア性組成物。
前記(D)成分が3-アミノプロピルトリメトキシシランである(17)に記載のガスバリア性組成物。
および
(ii)水酸基とカルボキシル基とを有する水溶性高分子(AB)
の少なくとも一方を含む水溶性高分子(X)と、
金属アルコキシドおよび/またはその加水分解縮合物(C)と、
エステル化触媒(E)と、を混合する、ガスバリア性組成物の製造方法であって、
前記水溶性高分子(X)100重量部に対し、460重量部以上、2700重量部以下の量で前記(C)成分を添加し、0.01重量部以上、100重量部以下の量で前記(E)成分を添加することにより、前記水溶性高分子(X)と前記(C)成分と前記(E)成分とを混合する工程を含む、ガスバリア性組成物の製造方法。
前記(A)成分と前記(B)成分との重量比が97/3から3/97となるように配合し、前記(A)成分と前記(B)成分との混合物100重量部に対し、460重量部以上、1600重量部以下の量で前記(C)成分を添加し、0.01重量部以上、100重量部以下の量で前記(E)成分を添加することにより、前記(A)成分と前記(B)成分と前記(C)成分と前記(E)成分とを混合する工程を含む、(21)に記載のガスバリア性組成物の製造方法。
前記水溶性高分子(X)と、前記(E)成分および前記(C)成分とを混合する工程を含み、
前記水溶性高分子(X)と、前記(E)成分および前記(C)成分とを混合する前記工程において、前記(C)成分の加水分解縮合反応を進行させる、(21)に記載のガスバリア性組成物の製造方法。
前記(A)成分および前記(B)成分を混合する工程と、
前記工程で得られた混合液と、前記(E)成分および前記(C)成分とを混合する工程と、
を含み、
前記混合液と、前記(E)成分および前記(C)成分とを混合する前記工程において、前記(C)成分の加水分解縮合反応を進行させる、(22)に記載のガスバリア性組成物の製造方法。
前記工程で得られた前記混合液および前記(C)成分を混合する工程と、を含み、
前記混合液および前記(C)成分を混合する前記工程において、前記(C)成分の加水分解縮合反応を進行させる、(26)に記載のガスバリア性組成物の製造方法。
前記工程で得られた前記混合液、前記(D)成分および前記(C)成分を混合する工程と、を含み、
前記混合液と前記(D)成分および前記(C)成分とを混合する前記工程において、前記(C)成分の加水分解縮合反応、ならびに前記(D)成分と金属酸化物およびカルボキシル基のうち少なくとも一方との反応を進行させる、(26)に記載のガスバリア性組成物の製造方法。
前記工程で得られた前記混合液と、前記(E)成分および前記(C)成分とを混合する工程と、を含み、
前記混合液、前記(E)成分および前記(C)成分を混合する前記工程において、前記(C)成分の加水分解縮合反応を進行させる、(26)に記載のガスバリア性組成物の製造方法。
前記工程で得られた前記混合液と前記(D)成分と前記(E)成分および前記(C)成分とを混合する工程と、を含み、
前記混合液、前記(D)成分、前記(E)成分および前記(C)成分を混合する前記工程において、前記(C)成分の加水分解縮合反応、ならびに前記(D)成分と金属酸化物およびカルボキシル基のうち少なくとも一方との反応を進行させる、(26)に記載のガスバリア性組成物の製造方法。
(1)乃至(20)のいずれかに記載のガスバリア性組成物の膜状物を形成し、これを熱処理するコーティング膜の製造方法。
(31)に記載の方法により製造されたコーティング膜。
なお、本発明において、「水酸基を有する水溶性高分子(A)」はカルボキシル基を有さず、「カルボキシル基を有する水溶性高分子(B)」は水酸基を有さない。
(i)水酸基を有する水溶性高分子(A)およびカルボキシル基を有する水溶性高分子(B)の混合物、
および
(ii)水酸基とカルボキシル基とを有する水溶性高分子(AB)
の少なくとも一方を含む水溶性高分子(X)と、
金属アルコキシドおよび/またはその加水分解縮合物(C)と、
エステル化触媒(E)と、を含む。
水酸基を有する水溶性高分子(A)と、
カルボキシル基を有する水溶性高分子(B)と、
金属アルコキシドおよび/またはその加水分解縮合物(C)と、
エステル化触媒(E)と、
を含むことが好ましい。
このガスバリア性組成物は、コーティング用の組成物として好適に用いられる。
さらに、本発明のガスバリア性組成物から得られるコーティング膜は、高温および高湿度条件下におけるガスバリア性の劣化が抑制される。
はじめに、ガスバリア性組成物の構成成分について説明する。
本発明において用いられる水溶性高分子(X)は、「(i)水酸基を有する水溶性高分子(A)およびカルボキシル基を有する水溶性高分子(B)の混合物」、および「(ii)水酸基とカルボキシル基とを有する水溶性高分子(AB)」の少なくとも一方を含んでなる。
(a)水酸基を有する水溶性高分子(A)およびカルボキシル基を有する水溶性高分子(B)の混合物
(b)水酸基とカルボキシル基とを有する水溶性高分子(AB)
(c)水酸基を有する水溶性高分子(A)および水酸基とカルボキシル基とを有する水溶性高分子(AB)の混合物
(d)カルボキシル基を有する水溶性高分子(B)および水酸基とカルボキシル基とを有する水溶性高分子(AB)の混合物
(e)水溶性高分子(A)および水溶性高分子(B)および水溶性高分子(AB)の混合物
本発明においては、「(a)水酸基を有する水溶性高分子(A)およびカルボキシル基を有する水溶性高分子(B)の混合物」を用いることが好ましい。
以下、(A)水酸基を有する水溶性高分子、(B)カルボキシル基を有する水溶性高分子、(AB)水酸基とカルボキシル基とを有する水溶性高分子について説明する。なお、以下の説明において、上記態様(a)~(e)を単に「水溶性高分子」と記載することもある。
本発明において用いられる水酸基を有する水溶性高分子(A)とは、水酸基をその高分子鎖中に少なくとも2個含む水溶性を示す高分子であって、好ましくは、ポリビニルアルコール、エチレン-ビニルアルコール共重合体等のポリビニルアルコールを含む共重合体、セルロース類およびその他の糖類からなる群から選ばれる一種以上の化合物である。これらは単独または二種以上用いてもよい。
本発明におけるカルボキシル基を有する水溶性高分子(B)とは、カルボキシル基をその高分子鎖中に少なくとも2個含む水溶性を示す高分子であって、たとえばポリカルボン酸である。カルボキシル基を有する水溶性高分子(B)は、好ましくは、ポリ(メタ)アクリル酸またはその部分中和物であり、さらに好ましくは分子内に少なくも2個以上のアクリル酸またはメタアクリル酸単位を有するポリマーであり、より好ましくは、アクリル酸またはメタアクリル酸の単一重合体(ポリアクリル酸またはポリメタアクリル酸)であっても、アクリル酸とメタアクリル酸の共重合体であっても、また他のモノマー単位を含む共重合体であってもよい。これらは単独または二種以上用いてもよい。
本発明において用いられる水酸基とカルボキシル基とを有する水溶性高分子(AB)とは、水酸基をその高分子鎖中に少なくとも1個含み、さらにカルボキシル基をその高分子鎖中に少なくとも1個含む水溶性を示す高分子である。
本発明における金属アルコキシドは、下記式(1)で表されるものを指す。
(R1)xM(OR2)y (1)
式中、R1で示される置換基は水素原子、アルキル基(たとえばメチル基、エチル基、プロピル基など)、アリール基(たとえばフェニル基、トリル基など)、炭素-炭素二重結合含有有機基(たとえばアクリロイル基、メタクリロイル基、ビニル基など)、ハロゲン含有基(たとえばクロロプロピル基、フルオロメチル基などのハロゲン化アルキル基など)などを表し、複数存在するR1は同一でも異なっていてもよい。R2は炭素数1以上、6以下、好ましくは炭素数1以上、4以下の低級アルキル基を表し、複数存在するOR2は同一でも異なっていてもよい。xおよびyは、x+y=4であり、さらにxは2以下となる整数を表す。また、(C)成分を構成するMは金属であり、具体的には、珪素、アルミニウム、ジルコニウム、チタニウムなどが例示され、それらを組み合わせて使ってもよい。なかでも珪素化合物は、比較的安価で入手しやすく、反応が緩やかに進行するため、工業的な利用価値が高い。
塗膜(コーティング膜、ハードコート)の耐擦傷性は、アルコキシ基の数に反映されることから、テトラメトキシシラン、テトラエトキシシラン等の4官能性金属アルコキシドを用いることが好ましい。また、これらの金属アルコキシド、金属アルコキシドの加水分解重縮合物は、単独または二種以上の混合物として用いてもよい。
(D)1分子中に金属酸化物と結合を形成できる官能基と、カルボキシル基と結合を形成できる官能基とをそれぞれ1つ以上有する化合物
本発明で用いられる、1分子中に金属酸化物と結合を形成できる官能基と、カルボキシル基と結合を形成できる官能基とをそれぞれ1つ以上有する化合物(D)は、有機材料である水溶性高分子(X)と、無機材料である(C)成分との材料分散性を向上させるために添加し、その使用により、より一層透明性の高い塗膜を得ることができる。
3-グリシドキシプロピルプロピルトリメトキシシラン、3-グリシドキシプロピルプロピルトリエトキシシラン、3-グリシドキシプロピルメチルジエトキシシラン等のグリシジル基とアルコキシシリル基とを有する化合物;
3-メルカプトプロピルメチルジメトキシシラン、3-メルカプトプロピルトリメトキシシラン等のチオール基とアルコキシシリル基とを有する化合物;
3-ウレイドプロピルトリメトキシシラン等のウレイド基とアルコキシシリル基とを有する化合物;等のアルコキシシリル基を有する化合物、2-アミノエタノール、3-アミノ-1-プロパノール、2-アミノ-1-アミノ-1-ブタノール、1-アミノ-2-ブタノール、2-アミノ-1-ブタノール,3-プロパンジオール、3-アミノ-1,2-プロパンジオール、4,2-(2-アミノエトキシ)エタノール、2-アミノ-2-メチル-1-プロパノール、4-アミノ-2-メチルブタノール、3-アミノプロピオン酸、2-アミノプロピオン酸、4-アミノ-n-ブチル酸、5-アミノ-n-バレリン酸、2-アミノイソバレリン酸、アスパラギン、アスパラギン酸、エチレンジアミン、2-アミノ-2-メチル-1,3-プロパンジオール、2-(2-アミノエチルアミノ)エタノール、2-アミノエタンチオール、2-アミノエタンスルホン酸、N,N-ジメチル-1,3-プロパンジアミン、N-(3-アミノプロピル)シクロヘキシルアミン、4-ピコリルアミン、3-ピコリルアミン、2-ピコリルアミン、4-(2-アミノエチル)ピリジン、3-(2-アミノエチル)ピリジン、4-アミノメチルピペリジン、1-アミノ-4-メチルピペラジン、3-アミノ-5-メチルピラゾール、1-(3-アミノプロピル)イミダゾール、2-アミノエタン-1-スルホン酸、3-アミノプロパンスルホン酸、スルファニル酸、1,4-ジアミノブタン二塩酸塩、1,5-ジアミノペンタン二塩酸塩等を挙げることができるが、これらに限定されるものではない。
本発明におけるエステル化触媒(E)とは、酸とアルコールからエステルを合成する反応を触媒する化合物のことである。酸は、有機酸または無機酸である。このような化合物であれば本発明のエステル化触媒(E)として用いることができるが、好ましくは無機酸の金属塩、有機酸の金属塩、有機リン化合物、カルボン酸およびその誘導体、スルホン酸およびその誘導体、鉱酸の有機アンモニウム塩またはピリジニウム塩、シアノ基含有有機化合物、イソシアノ基含有有機化合物、ケテン誘導体、ジカルコゲニド化合物、塩化シアヌル、カルボニルジイミダゾール、ヘキサクロロアセトンが挙げられる。
具体的には、たとえばプロピオニトリル、マロノニトリル、ベンゾニトリルなどの炭素数1以上、30以下の脂肪族または芳香族ニトリル化合物類;
トリクロロアセトニトリル、ブロモアセトニトリルp-クロロベンゾニトリルなどの炭素数1以上、30以下のハロゲン化脂肪族または芳香族ニトリル化合物類;
シアノピリジン、トリス(2-シアノエチル)ニトロメタンなどの炭素数1以上、30以下の含窒素脂肪族または芳香族ニトリル化合物類;
シアノメチルベンゼンスルホナートなどの炭素数1以上、30以下の含硫黄脂肪族または芳香族ニトリル化合物類;
ジシアノジアミド、1-シアノイソウレア、N-シアノホルムアミド、N-シアノアセトアミド、1-シアノベンゾトリアゾール、1-ピロリジンカルボニトリル、4-モルホリンカルボニトリルなどの炭素数1以上、50以下の脂肪族または芳香族N-シアノ化合物類;
シアン酸-p-トリルなどの炭素数1以上、50以下の脂肪族または芳香族O-シアノ化合物類;
テトラエチルアンモニウムシアナート、ピリジニウムシアナートなどのシアン酸アンモニウム塩またはピリジニウム塩;等が挙げられる。
具体的には、たとえばイソシアン化シクロヘキシル、イソプロピルイソシアニド、2,6-ジメチルフェニルイソシアニドなどの炭素数1以上、30以下の脂肪族または芳香族イソシアノ化合物類;2-モルホリノエチルイソシアニド、ジエチルイソシアノメチルホスホナート、エチルイソシアノアセテートなどの炭素数1以上、30以下のヘテロ原子含有脂肪族または芳香族イソシアノ化合物類;などが挙げられる。
(B)成分:ポリ(メタ)アクリル酸またはその部分中和物であって、
(C)成分:アルコキシシラン、アルコキシジルコニウム、アルコキシアルミニウムおよびアルコキシチタンからなる群から選ばれる一種以上および/またはその加水分解縮合物
(E)成分:エステル化触媒
(B)成分:ポリアクリル酸
(C)成分:テトラメトキシシラン
(E)成分:ジシアノジアミド
(A)成分:ポリビニルアルコール、エチレン-ビニルアルコール共重合体、および糖類からなる群から選ばれる一種以上の化合物
(B)成分:ポリ(メタ)アクリル酸またはその部分中和物であって、
(C)成分:アルコキシシラン、アルコキシジルコニウム、アルコキシアルミニウムおよびアルコキシチタンからなる群から選ばれる一種以上および/またはその加水分解縮合物
(D)成分:3-アミノプロピルトリメトキシシランおよび3-アミノプロピルトリエトキシシランからなる群から選択される一種以上
(E)成分:エステル化触媒
(B)成分:ポリアクリル酸
(C)成分:テトラメトキシシラン
(D)成分:3-アミノプロピルトリメトキシシランまたは3-アミノプロピルトリエトキシシラン
(E)成分:ジシアノジアミド
本発明におけるガスバリア性組成物は、「(i)水酸基を有する水溶性高分子(A)およびカルボキシル基を有する水溶性高分子(B)の混合物」、および「(ii)水酸基とカルボキシル基とを有する水溶性高分子(AB)」の少なくとも一方を含む水溶性高分子(X)と、金属アルコキシドおよび/または金属アルコキシドの加水分解縮合物(C)と、エステル化触媒(E)とを必須成分とする。以下、これらの成分の配合を説明する。
たとえば、本発明のガスバリア性組成物は、金属アルコキシドの加水分解・重縮合反応における反応を促進させる目的で、以下に示すような加水分解・重合反応の触媒となりうるものを含んでいてもよい。金属アルコキシドの加水分解・重合反応の触媒として使用されるものは、「最新ゾル-ゲル法による機能性薄膜作製技術」(平島碩著、株式会社総合技術センター、P29)や「ゾル-ゲル法の科学」(作花済夫著、アグネ承風社、P154)等に記載されている一般的なゾル-ゲル反応で用いられる触媒である。
金属酸化物微粒子の具体例として下記がある。
本発明のガスバリア性組成物は、さらに溶媒を含んでもよい。溶媒を含むことにより、ガスバリア性組成物からなるコート材料を樹脂表面に塗布する工程を容易にするので好ましい。
メタノール、エタノール、プロパノールなどの炭素数1以上30以下のアルコール類;
n-ヘキサン、n-ヘプタン、トルエン、キシレンなどの炭素数4以上30以下の脂肪族または芳香族炭化水素;
ジクロロメタン、クロロホルム、クロロベンゼン、o-ジブロモベンゼンなどの炭素数1以上30以下の含ハロゲン脂肪族または芳香族炭化水素;
ジエチルエーテル、ジフェニルエーテルなどの炭素数2以上30以下の脂肪族または芳香族エーテル類;
酢酸エチル、プロピオン酸ブチルなどの炭素数2以上30以下の脂肪族または芳香族エステル類;
ジメチルホルムアミド、ジメチルアセトアミドなどの炭素数2から30の脂肪族または芳香族アミド化合物;
アセトニトリル、ベンゾニトリルなどの炭素数2以上30以下の脂肪族または芳香族ニトリル類;等が挙げられる。これらの溶媒は単独で用いてもまた二種類以上の混合溶媒として用いてもよい。
本発明におけるガスバリア性組成物は、「(i)水酸基を有する水溶性高分子(A)およびカルボキシル基を有する水溶性高分子(B)」、および「(ii)水酸基とカルボキシル基とを有する水溶性高分子(AB)」の少なくとも一方を含む水溶性高分子(X)と、金属アルコキシドおよび/またはその加水分解縮合物(C)と、エステル化触媒(E)とを混合することにより得ることができる。
(a)水溶性高分子(X)、(D)成分および(E)成分を溶媒中で混合する工程、および
前工程で得られた混合液および前記(C)成分を混合する工程を含み、
混合液および(C)成分を混合する工程において、(C)成分の加水分解縮合反応を進行させる方法。
前工程で得られた混合液、(D)成分および(C)成分を混合する工程を含み、
混合液、(D)成分および(C)成分を混合する工程において、(C)成分の加水分解縮合反応、ならびに(D)成分と金属酸化物およびカルボキシル基のうち少なくとも一方との反応を進行させる方法。
前工程で得られた混合液、前記(E)成分および前記(C)成分を混合する工程を含み、
混合液、(E)成分および(C)成分を混合する工程において、(C)成分の加水分解縮合反応を進行させる方法。
前工程で得られた混合液、(D)成分、(E)成分および(C)成分を混合する工程を含み、
混合液、(D)成分、(E)成分および(C)成分を混合する工程において、(C)成分の加水分解縮合反応、ならびに(D)成分と金属酸化物およびカルボキシル基のうち少なくとも一方との反応を進行させる方法。
前工程で得られた混合液および前記(C)成分に触媒および水を添加し、一定時間攪拌した溶液を混合する工程を含み、
混合液、および(C)成分に触媒および水を添加し、一定時間攪拌した溶液を混合する工程において、(C)成分の加水分解縮合反応をさらに進行させる方法。
前工程で得られた混合液、(D)成分、および(C)成分に触媒および水を添加し、一定時間攪拌した溶液を混合する工程を含み、
混合液、(D)成分、および(C)成分に触媒および水を添加し、一定時間攪拌した溶液を混合する工程において、(C)成分の加水分解縮合反応をさらに進行させるとともに、(D)成分と金属酸化物およびカルボキシル基のうち少なくとも一方との反応を進行させる方法。
前工程で得られた混合液、前記(E)成分、および前記(C)成分に触媒および水を添加し、一定時間攪拌した溶液を混合する工程を含み、
混合液、(E)成分、および(C)成分に触媒および水を添加し、一定時間攪拌した溶液を混合する工程において、(C)成分の加水分解縮合反応をさらに進行させる方法。
前工程で得られた混合液、(D)成分、(E)成分、および(C)成分に触媒および水を添加し、一定時間攪拌した溶液を混合する工程を含み、
混合液、(D)成分、(E)成分、および(C)成分に触媒および水を添加し、一定時間攪拌した溶液を混合する工程において、(C)成分の加水分解縮合反応をさらに進行させるとともに、(D)成分と金属酸化物およびカルボキシル基のうち少なくとも一方との反応を進行させる方法。
本発明におけるガスバリア性組成物は、水酸基を有する水溶性高分子(A)、カルボキシル基を有する水溶性高分子(B)、金属アルコキシドおよび/またはその加水分解縮合物(C)およびエステル化触媒(E)を混合することにより得ることができる。
なお、本発明におけるガスバリア性組成物の製造方法は、(A)成分と(B)成分との重量比が97/3から3/97となるように配合するとともに、(A)成分と(B)成分との混合物100重量部に対し、(C)成分を460重量部以上、1600重量部以下、前記(E)成分を0.01重量部以上、100重量部以下の量となるように添加する工程を含む。
(i)(A)成分、(B)成分、(D)成分および(E)成分を溶媒中で混合する工程、および
前工程で得られた混合液および前記(C)成分を混合する工程を含み、
混合液および(C)成分を混合する工程において、(C)成分の加水分解縮合反応を進行させる方法。
前工程で得られた混合液、(D)成分および(C)成分を混合する工程を含み、
混合液、(D)成分および(C)成分を混合する工程において、(C)成分の加水分解縮合反応、ならびに(D)成分と金属酸化物およびカルボキシル基のうち少なくとも一方との反応を進行させる方法。
前工程で得られた混合液、前記(E)成分および前記(C)成分を混合する工程を含み、
混合液、(E)成分および(C)成分を混合する工程において、(C)成分の加水分解縮合反応を進行させる方法。
前工程で得られた混合液、(D)成分、(E)成分および(C)成分を混合する工程を含み、
混合液、(D)成分、(E)成分および(C)成分を混合する工程において、(C)成分の加水分解縮合反応、ならびに(D)成分と金属酸化物およびカルボキシル基のうち少なくとも一方との反応を進行させる方法。
前工程で得られた混合液および前記(C)成分に触媒および水を添加し、一定時間攪拌した溶液を混合する工程を含み、
混合液、および(C)成分に触媒および水を添加し、一定時間攪拌した溶液を混合する工程において、(C)成分の加水分解縮合反応をさらに進行させる方法。
前工程で得られた混合液、(D)成分、および(C)成分に触媒および水を添加し、一定時間攪拌した溶液を混合する工程を含み、
混合液、(D)成分、および(C)成分に触媒および水を添加し、一定時間攪拌した溶液を混合する工程において、(C)成分の加水分解縮合反応をさらに進行させるとともに、(D)成分と金属酸化物およびカルボキシル基のうち少なくとも一方との反応を進行させる方法。
前工程で得られた混合液、前記(E)成分、および前記(C)成分に触媒および水を添加し、一定時間攪拌した溶液を混合する工程を含み、
混合液、(E)成分、および(C)成分に触媒および水を添加し、一定時間攪拌した溶液を混合する工程において、(C)成分の加水分解縮合反応をさらに進行させる方法。
前工程で得られた混合液、(D)成分、(E)成分、および(C)成分に触媒および水を添加し、一定時間攪拌した溶液を混合する工程を含み、
混合液、(D)成分、(E)成分、および(C)成分に触媒および水を添加し、一定時間攪拌した溶液を混合する工程において、(C)成分の加水分解縮合反応をさらに進行させるとともに、(D)成分と金属酸化物およびカルボキシル基のうち少なくとも一方との反応を進行させる方法。
本発明のコーティング膜は、本発明のガスバリア性組成物の膜状物を形成しこれを熱処理することにより製造される。
膜状物とは、組成物が基材の表面を覆った状態を指す。膜状物を形成する方法は、特に限定はなく、たとえばガスバリア性組成物の溶液をガラス板、金属板や熱可塑性樹脂フィルムなどの支持体上に流延し、乾燥する方法などがある。支持体上に所望の厚さに膜状物を形成した後、熱処理を行う。熱処理温度は通常50℃以上、250℃以下の範囲であって、より好ましくは80℃以上、200℃以下、さらに好ましくは80℃以上、150℃以下の範囲である。本発明において、(E)エステル化触媒を使用することにより、たとえば、より低温で高いガスバリア性を発現することも可能となる。より低温で熱処理することにより、コーティング膜の着色を抑制できる。また熱可塑性樹脂フィルムを支持体として用いる場合、低融点の樹脂フィルム上に、コーティング膜を製造することも可能である。熱処理時間は通常1秒以上である。
一方、同様の方法にて測定されたコーティング膜の酸素透過率(cc/m2・day・atm)は、23以下、好ましくは18以下である。なお、酸素透過率の下限値は0.01以上とすることができる。
一方、同様の方法にて測定された湿熱試験後のコーティング膜の酸素透過率は、30以下、好ましくは23以下、より好ましくは18以下である。なお、酸素透過率の下限値は0.01以上とすることができる。
(i)基板上に、本発明のコーティング膜を積層した積層体、および
(ii)本発明のコーティング膜と、プラスチック基材とを積層した積層体
(iii)プラスチック基材と、このプラスチック基材上に形成された無機化合物からなる蒸着膜と、この蒸着膜上に形成された本発明のコーティング膜と、を備える積層体
等が挙げられる。
蒸着膜としては、AlO、SiN、SiO、ダイヤモンド・ライク・カーボン(Diamond-like
Carbon)等からなる膜を用いることができ、これらは組み合わせて用いることができる。蒸着膜の形成方法としては、公知の方法を用いることができ、物理気相成長法(Physical
Vapor Deposition)、化学気相成長法(Chemical Vapor
Deposition)等を挙げることができる。
従来から、紫外線領域の光を吸収して発色または変色する、いわゆるフォトクロミック化合物が知られている。このフォトクロミック化合物を樹脂に添加したフォトクロミック化合物含有樹脂は、幅広く利用されており、たとえば、ガラス間に薄膜状に形成し、自動車用ガラス、窓ガラスに使用されている。また、メガネレンズ材料に練り混んだり、レンズ上に積層することで、フォトクロミックレンズとして使用されている。
フォトクロミックレンズとは、屋外では、太陽光に含まれる紫外光により、速やかに着色し、サングラスとして機能し、屋内では、退色して透明な通常のメガネとして機能するレンズのことである。これらフォトクロミック製品は、紫外光の照射に応じた発色-退色作用が持続しないという問題点がある。原因は、紫外光や、大気中の酸素および水分との接触によるフォトクロミック化合物の劣化と見られている。そのため、これら製品は、多湿下で長時間使用しても発色-退色作用が持続できる耐久性が要求される。
本発明のコーティング材料からなるフィルムは、高温および高湿度条件下におけるガスバリア性の劣化が抑制されている。そのため、フォトクロミック製品上に本発明のフィルムを積層すれば、ガスバリア性が長期に亘って維持され、大気中のガスを遮断し、フォトクロミック化合物の劣化を抑制できると考えられる。特にフォトクロミックレンズにおいては、レンズの傷つき防止のため、ハードコート層が積層されるが、本発明のコーティング膜は、ガスバリア能に加えて、ハードコート能を有しているため、ハードコート膜の積層は不要となる。
ディスプレイ用基板は、従来ガラスが用いられていたが、近年、ディスプレイの小型化、軽量化に対応するため、薄い、軽い、割れないといった特徴を持つプラスチックに置き換わっている。プラスチックは上記のような特徴を持つ反面、ガスバリア性、寸法安定性、耐熱性、耐薬品性、低吸水率性、光学異方性等、耐擦傷性に問題を抱えている。特にガスバリア性は、水蒸気、酸素の表示素子内への侵入によって、表示欠陥等の問題を引き起こすために、高い性能が要求される。本発明のコーティング膜をディスプレイ基板上に積層すれば、高温および高湿度条件下であってもガスバリア性が維持されるので、長期間に亘り大気中のガスを遮断し、表示素子の劣化を抑制することができる。また、併せてハードコート能を基板に付与することができる。
(ガスバリア性(ハードコート用)組成物の調製)
ポリビニルアルコール水溶液
(A)成分として、和光純薬工業社製ポリビニルアルコール(PVA)500、完全ケン化型(平均重合度:約400~600)5重量部に対して蒸留水95重量部を加えPVAを加熱下溶解することでPVA5重量%水溶液を得た。
ポリアクリル酸水溶液
(B)成分として、和光純薬工業社製ポリアクリル酸(PAA)水溶液(25%)(粘度:8000~12000cP(30℃))20重量部に対して蒸留水30重量部を加えPAA10重量%水溶液を得た。
なお、以降の実施例および比較例において、(A)成分を含む水溶液および(B)成分を含む水溶液として、それぞれこれらの水溶液を用いた。
メタノール771重量部に、(C)成分であるテトラメトキシシラン(TMOS)460重量部、(E)成分であるジシアノジアミドを23重量部加え、その後ジシアノジアミドが溶解するまで攪拌した。これを溶液(1)とする。
PVA5重量%水溶液600重量部にPAA10重量%水溶液700重量部、水838重量部を加えた後、この水溶液を攪拌しながら、(D)成分である3-アミノプロピルトリメトキシシラン(APTMOS)とエタノールを重量比1:9で混合した溶液52重量部を滴下し、さらに室温で30分攪拌した。これを溶液(2)とする。
溶液(2)に溶液(1)を加え、30℃で1.5時間攪拌し、ガスバリア性組成物を得た。
厚さ50μmのポリイミドフィルム(東レ・デュポン株式会社製、カプトン200EN 膜厚50μm)に、上記の方法で調製した組成物を、バーコーターを用いて、硬化後の厚みが約0.7μmとなるように塗布した。その後、40℃で10分、110℃で2時間加熱し、コーティング膜を得た。
メタノール778重量部に、(C)成分であるテトラメトキシシラン(TMOS)460重量部、(E)成分であるジシアノジアミドを23重量部加え、その後ジシアノジアミドが溶解するまで攪拌した。これを溶液(3)とする。
PVA5重量%水溶液1000重量部にPAA10重量%水溶液500重量部、水624重量部を加えた後、この水溶液を攪拌しながら、(D)成分である3-アミノプロピルトリメトキシシラン(APTMOS)とエタノールを重量比1:9で混合した溶液37重量部を滴下し、さらに室温で30分攪拌した。これを溶液(4)とする。
溶液(4)に溶液(3)を加え、30℃で1.5時間攪拌し、ガスバリア性組成物を得た。これを用いて、実施例1と同様の方法で塗布、加熱し、コーティング膜を得た。
メタノール775重量部に、(C)成分であるテトラメトキシシラン(TMOS)465重量部、(E)成分であるジシアノジアミドを23重量部加え、その後ジシアノジアミドが溶解するまで攪拌した。これを溶液(5)とする。
PVA5重量%水溶液600重量部にPAA10重量%水溶液700重量部、水851重量部を加えた後、この水溶液を攪拌しながら、(D)成分である3-アミノプロピルトリメトキシシラン(APTMOS)とエタノールを重量比1:9で混合した溶液52重量部を滴下し、さらに室温で30分攪拌した。これを溶液(6)とする。
溶液(6)に溶液(5)を加え、30℃で1.5時間攪拌し、ガスバリア性組成物を得た。これを用いて、実施例1と同様の方法で塗布、加熱し、コーティング膜を得た。
メタノール810重量部に、(C)成分であるテトラメトキシシラン(TMOS)500重量部、(E)成分であるジシアノジアミドを23重量部加え、その後ジシアノジアミドが溶解するまで攪拌した。これを溶液(7)とする。
PVA5重量%水溶液1000重量部にPAA10重量%水溶液500重量部、水728重量部を加えた後、この水溶液を攪拌しながら、(D)成分である3-アミノプロピルトリメトキシシラン(APTMOS)とエタノールを重量比1:9で混合した溶液37重量部を滴下し、さらに室温で30分攪拌した。これを溶液(8)とする。
溶液(8)に溶液(7)を加え、30℃で1.5時間攪拌し、ガスバリア性組成物を得た。これを用いて、実施例1と同様の方法で塗布、加熱し、コーティング膜を得た。
メタノール824重量部に、(C)成分であるテトラメトキシシラン(TMOS)528重量部、(E)成分であるジシアノジアミドを23重量部加え、その後ジシアノジアミドが溶解するまで攪拌した。これを溶液(9)とする。
PVA5重量%水溶液600重量部にPAA10重量%水溶液700重量部、水1013重量部を加えた後、この水溶液を攪拌しながら、(D)成分である3-アミノプロピルトリメトキシシラン(APTMOS)とエタノールを重量比1:9で混合した溶液52重量部を滴下し、さらに室温で30分攪拌した。これを溶液(10)とする。
溶液(10)に溶液(9)を加え、30℃で1.5時間攪拌し、ガスバリア性組成物を得た。これを用いて、実施例1と同様の方法で塗布、加熱し、コーティング膜を得た。
メタノール867重量部に、(C)成分であるテトラメトキシシラン(TMOS)581重量部、(E)成分であるジシアノジアミドを23重量部加え、その後ジシアノジアミドが溶解するまで攪拌した。これを溶液(11)とする。
PVA5重量%水溶液600重量部にPAA10重量%水溶液700重量部、水1152重量部を加えた後、この水溶液を攪拌しながら、(D)成分である3-アミノプロピルトリメトキシシラン(APTMOS)とエタノールを重量比1:9で混合した溶液52重量部を滴下し、さらに室温で30分攪拌した。これを溶液(12)とする。
溶液(12)に溶液(11)を加え、30℃で1.5時間攪拌し、ガスバリア性組成物を得た。これを用いて、実施例1と同様の方法で塗布、加熱し、コーティング膜を得た。
メタノール1146重量部に、(C)成分であるテトラメトキシシラン(TMOS)933重量部、(E)成分であるジシアノジアミドを23重量部加え、その後ジシアノジアミドが溶解するまで攪拌した。これを溶液(13)とする。
PVA5重量%水溶液600重量部にPAA10重量%水溶液700重量部、水2066重量部を加えた後、この水溶液を攪拌しながら、(D)成分である3-アミノプロピルトリメトキシシラン(APTMOS)とエタノールを重量比1:9で混合した溶液52重量部を滴下し、さらに室温で30分攪拌した。これを溶液(14)とする。
溶液(14)に溶液(13)を加え、30℃で1.5時間攪拌し、ガスバリア性組成物を得た。これを用いて、実施例1と同様の方法で塗布、加熱し、コーティング膜を得た。
図2に、コーティング膜の断面TEM画像を示す。
(PET/SiN積層膜の作製)
厚み125μmのPET(ポリエチレンテレフタレート)フィルム上に、シリコーン樹脂コート剤(商品名:SHC900
GE東芝製)を厚み2μmとなるようにグラビアコーティングし、120℃で15分加熱し、コート膜を得た。続いて、シリコーン樹脂層上に、CVD法により、膜厚20nmとなるように窒化珪素(SiN)膜の作製を行った。以後、ここで得られたものをPET/SiN積層膜と略記する。
メタノール1142重量部に、(C)成分であるテトラメトキシシラン(TMOS)930重量部、(E)成分であるジシアノジアミドを22.3重量部加え、その後ジシアノジアミドが溶解するまで攪拌した。これを溶液(15)とする。
PVA5重量%水溶液600重量部にPAA10重量%水溶液700重量部、水2055重量部を加えた後、この水溶液を攪拌しながら、(D)成分である3-アミノプロピルトリメトキシシラン(APTMOS)とエタノールを重量比1:9で混合した溶液52重量部を滴下し、さらに室温で30分攪拌した。これを溶液(16)とする。
溶液(16)に溶液(15)を加え、30℃で1.5時間攪拌し、ガスバリア性組成物を得た。
PET/SiN積層膜に、上記の方法で調製した組成物を、バーコーターを用いて、硬化後の厚みが約2μmとなるように塗布した。その後、40℃で10分、110℃で2時間加熱し、コーティング膜を得た。
メタノール1052重量部に、(C)成分であるテトラメトキシシラン(TMOS)830重量部、(E)成分であるジシアノジアミドを11.4重量部加え、その後ジシアノジアミドが溶解するまで攪拌した。これを溶液(17)とする。
PVA5重量%水溶液1400重量部にPAA10重量%水溶液300重量部、水1286重量部を加え、さらに室温で30分攪拌した。これを溶液(18)とする。
溶液(18)に溶液(17)を加え、30℃で1.5時間攪拌し、ガスバリア性組成物を得た。これを用いて、実施例8と同様の方法でPET/SiN積層膜上に塗布、加熱し、コーティング膜を得た。
メタノール1437重量部に、(C)成分であるテトラメトキシシラン(TMOS)1300重量部、(E)成分であるジシアノジアミドを23重量部加え、その後ジシアノジアミドが溶解するまで攪拌した。これを溶液(19)とする。
PVA5重量%水溶液600重量部にPAA10重量%水溶液700重量部、水3018重量部を加えた後、この水溶液を攪拌しながら、(D)成分である3-アミノプロピルトリメトキシシラン(APTMOS)とエタノールを重量比1:9で混合した溶液52重量部を滴下し、さらに室温で30分攪拌した。これを溶液(20)とする。
溶液(20)に溶液(19)を加え、30℃で1.5時間攪拌し、ガスバリア性組成物を得た。これを用いて、実施例1と同様の方法で塗布、加熱し、コーティング膜を得た。
メタノール1674重量部に、(C)成分であるテトラメトキシシラン(TMOS)1600重量部、(E)成分であるジシアノジアミドを23重量部加え、その後ジシアノジアミドが溶解するまで攪拌した。これを溶液(21)とする。
PVA5重量%水溶液600重量部にPAA10重量%水溶液700重量部、水3797重量部を加えた後、この水溶液を攪拌しながら、(D)成分である3-アミノプロピルトリメトキシシラン(APTMOS)とエタノールを重量比1:9で混合した溶液52重量部を滴下し、さらに室温で30分攪拌した。これを溶液(22)とする。
溶液(22)に溶液(21)を加え、30℃で1.5時間攪拌し、ガスバリア性組成物を得た。これを用いて、実施例1と同様の方法で塗布、加熱し、コーティング膜を得た。
PAA10重量%水溶液700重量部を攪拌しながら、(D)成分である3-アミノプロピルトリメトキシシランとエタノールを重量比1:9で混合した溶液を52重量部滴下し、その後室温で30分攪拌した。続いて、PVA5重量%水溶液を600重量部、(E)成分であるジシアノジアミドを23重量部、水1013重量部を加えてさらに10分間攪拌した。続いて、(C)成分であるテトラメトキシシラン528重量部、メタノール824重量部を添加し、30℃で1.5時間攪拌し、ガスバリア性組成物を得た。これを用いて、実施例1と同様の方法で塗布、加熱し、コーティング膜を得た。
PAA10重量%水溶液700重量部に、PVA5重量%水溶液を600重量部、(E)成分であるジシアノジアミド23重量部、水1013重量部を加えて10分間攪拌した。これを溶液(23)とする。一方、(C)成分であるテトラメトキシシラン528重量部に、メタノール824重量部、(D)成分である3-アミノプロピルトリメトキシシランとエタノールを重量比1:9で混合した溶液52重量部を添加し、その後室温で10分攪拌した。これを溶液(24)とする。
溶液(24)と溶液(23)を混合し、さらに室温で1.5時間攪拌を行った。これを用いて、実施例1と同様の方法で塗布、加熱し、コーティング膜を得た。
PAA10重量%水溶液700重量部とPVA5重量%水溶液600重量部、水1013重量部を混合した。これを溶液(25)とする。一方、(C)成分であるテトラメトキシシラン528重量部に、(D)成分である3-アミノプロピルトリメトキシシランとエタノールを重量比1:9で混合した溶液を52重量部、(E)成分であるジシアノジアミド23重量部、メタノール824重量部を添加し、その後室温で30分攪拌した。これを溶液(26)とする。
溶液(26)と溶液(25)を混合し、さらに室温で1.5時間攪拌を行った。これを用いて、実施例1と同様の方法で塗布、加熱し、コーティング膜を得た。
メタノール609重量部に、(C)成分であるテトラメトキシシラン(TMOS)256重量部、(E)成分であるジシアノジアミドを23重量部加え、その後ジシアノジアミドが溶解するまで攪拌した。これを溶液(27)とする。
PVA5重量%水溶液600重量部にPAA10重量%水溶液700重量部、水309重量部を加えた後、この水溶液を攪拌しながら、(D)成分である3-アミノプロピルトリメトキシシラン(APTMOS)とエタノールを重量比1:9で混合した溶液52重量部を滴下し、さらに室温で30分攪拌した。これを溶液(28)とする。
溶液(28)に溶液(27)を加え、30℃で1.5時間攪拌し、ガスバリア性組成物を得た。これを用いて、実施例1と同様の方法で塗布、加熱し、コーティング膜を得た。
図3に、コーティング膜の断面TEM画像を示す。
メタノール708重量部に、(C)成分であるテトラメトキシシラン(TMOS)382重量部、(E)成分であるジシアノジアミドを23重量部加え、その後ジシアノジアミドが溶解するまで攪拌した。これを溶液(29)とする。
PVA5重量%水溶液600重量部にPAA10重量%水溶液700重量部、水634重量部を加えた後、この水溶液を攪拌しながら、(D)成分である3-アミノプロピルトリメトキシシラン(APTMOS)とエタノールを重量比1:9で混合した溶液52重量部を滴下し、さらに室温で30分攪拌した。これを溶液(30)とする。
溶液(30)に溶液(29)を加え、30℃で1.5時間攪拌し、ガスバリア性組成物を得た。これを用いて、実施例1と同様の方法で塗布、加熱し、コーティング膜を得た。
メタノール762重量部に、(C)成分であるテトラメトキシシラン(TMOS)450重量部、(E)成分であるジシアノジアミドを23重量部加え、その後ジシアノジアミドが溶解するまで攪拌した。これを溶液(31)とする。
PVA5重量%水溶液600重量部にPAA10重量%水溶液700重量部、水812重量部を加えた後、この水溶液を攪拌しながら、(D)成分である3-アミノプロピルトリメトキシシラン(APTMOS)とエタノールを重量比1:9で混合した溶液52重量部を滴下し、さらに室温で30分攪拌した。これを溶液(32)とする。
溶液(32)に溶液(31)を加え、30℃で1.5時間攪拌し、ガスバリア性組成物を得た。これを用いて、実施例1と同様の方法で塗布、加熱し、コーティング膜を得た。
シリカ含有率は、以上の実施例および比較例における(C)成分が100%反応し、SiO2になったと仮定して算出した。たとえば、(C)成分がTMOSの場合100%反応し、SiO2になったと仮定して算出した。すなわち
TMOS:Mw=152
SiO2:Mw=60
より、
SiO2/TMOS=60/152=0.395
である。つまり、TMOSの添加量に0.395を掛けた値が、膜中のSiO2含量となる。これより、シリカ(SiO2)含有率は、以下の式を用いて計算した。
シリカ(SiO2)含有率=[TMOS]*0.395/([A]+[B]+([TMOS]*0.395)+[E]+[D])*100
ただし、上記式において、[A]、[B]、[TMOS]、[E]、[D]はそれぞれの成分の重量部を示す
シリカ(SiO2)含有率=(460*0.395)/(30+70+(460*0.395)+23+5.2)*100=58.6(小数点第2位以下四捨五入)
である。
以上の実施例および比較例におけるコーティング膜について、以下の方法で物性評価を行った。評価結果を表1に示す。
23℃、90%RH雰囲気下で、酸素透過率測定装置(MOCON社製 OXTRAN 2/21MH)を用いて酸素透過率(cc/m2・day・atm)を測定した。
上記のようにして酸素透過率を測定した後、サンプルを装置から取り出し、湿熱試験(温度40℃、湿度90%の条件下24時間放置)を行った。その後再び酸素透過率測定装置にセットし、酸素透過率(cc/m2・day・atm)を測定した。
(1-1)水酸基を有する水溶性高分子(A)、カルボン酸(カルボキシル基)を有する水溶性高分子(B)、金属アルコキシドおよび/またはそれらの加水分解縮合物(C)、1分子中に金属酸化物と結合を形成できる官能基と、カルボキシル基と結合を形成できる官能基をそれぞれ1つ以上有する化合物(D)からなり、(A)と(B)の重量比が97/3から3/97、(A)と(B)の混合物100重量部に対し、(C)460重量部以上、1600重量部以下、(D)0.1重量部以上、20重量部以下であるガスバリア性ハードコート用組成物(ガスバリア性組成物)。
Claims (24)
- (i)水酸基を有する水溶性高分子(A)およびカルボキシル基を有する水溶性高分子(B)の混合物、
および
(ii)水酸基とカルボキシル基とを有する水溶性高分子(AB)
の少なくとも一方を含む水溶性高分子(X)と、
金属アルコキシドおよび/またはその加水分解縮合物(C)と、
エステル化触媒(E)と、を含み、
前記水溶性高分子(X)100重量部に対し、前記(C)成分を460重量部以上、2700重量部以下、前記(E)成分を0.01重量部以上、100重量部以下含む、ガスバリア性組成物。 - 水酸基を有する水溶性高分子(A)と、
カルボキシル基を有する水溶性高分子(B)と、
金属アルコキシドおよび/またはその加水分解縮合物(C)と、
エステル化触媒(E)と、を含み、
前記(A)成分と前記(B)成分との重量比が97/3から3/97であって、
前記(A)成分と前記(B)成分との混合物100重量部に対し、前記(C)成分を460重量部以上、1600重量部以下、前記(E)成分を0.01重量部以上、100重量部以下含む、請求項1に記載のガスバリア性組成物。 - 1分子中に金属酸化物と結合を形成できる官能基と、カルボキシル基と結合を形成できる官能基とをそれぞれ1つ以上有する化合物(D)をさらに含み、
前記水溶性高分子(X)100重量部に対し、前記(D)成分を0.1重量部以上、20重量部以下含む請求項1に記載のガスバリア性組成物。 - 前記(D)成分において、
金属酸化物と結合を形成できる前記官能基が、アルコキシシリル基、シラノール基、水酸基、カルボキシル基、アミノ基およびアンモニウム基からなる群から選択される一種以上の基であって、
カルボキシル基と結合を形成できる前記官能基が、アミノ基、エポキシ基、チオール基、水酸基、ウレタン結合基、尿素結合基およびアンモニウム基からなる群から選択される一種以上の基である請求項3に記載のガスバリア性組成物。 - 前記(E)成分が、無機酸の金属塩、有機酸の金属塩、有機リン化合物、カルボン酸およびその誘導体、スルホン酸およびその誘導体、鉱酸の有機アンモニウム塩またはピリジニウム塩、シアノ基含有有機化合物、イソシアノ基含有有機化合物、ケテン誘導体、ジカルコゲニド化合物、塩化シアヌル、カルボニルジイミダゾールおよびヘキサクロロアセトンからなる群から選ばれる一種以上の化合物である請求項1乃至4いずれかに記載のガスバリア性組成物。
- 前記(A)成分が、ポリビニルアルコール、エチレン-ビニルアルコール共重合体、および糖類からなる群から選ばれる一種以上の化合物である請求項1乃至5のいずれかに記載のガスバリア性組成物。
- 前記(B)成分が、ポリ(メタ)アクリル酸またはその部分中和物である請求項1乃至6いずれかに記載のガスバリア性組成物。
- 前記(C)成分の前記金属アルコキシドが、下記一般式(1)で表される請求項1乃至7のいずれかに記載のガスバリア性組成物;
(R1)xM(OR2)y (1)
(式中、Mは、珪素、アルミニウム、ジルコニウムまたはチタニウムを表す。R1は水素原子、アルキル基、アリール基、アクリロイル基、メタクリロイル基、ビニル基またはハロゲン化アルキル基を表し、複数存在するR1は同一でも異なっていてもよい。R2は炭素数1以上、6以下の低級アルキル基を表し、複数存在するOR2基は同一でも異なっていてもよい。xおよびyは、x+y=4でありかつ、xは2以下となる整数を表す。)。 - 前記(C)成分が、アルコキシシラン、アルコキシジルコニウム、アルコキシアルミニウムおよびアルコキシチタンからなる群から選ばれる一種以上である請求項8に記載のガスバリア性組成物。
- 前記(C)成分が、アルコキシシランの縮合物、アルコキシジルコニウムの縮合物、アルコキシアルミニウムの縮合物、およびアルコキシチタンの縮合物からなる群から選択される一種以上である請求項8に記載のガスバリア性組成物。
- 前記(C)成分が、水および触媒の添加によりゾルゲル反応することで、金属酸化物となる化合物である、請求項8乃至10のいずれかに記載のガスバリア性組成物。
- 平均粒径が100nm以下の金属酸化物微粒子をさらに含み、当該ガスバリア性組成物100重量部に対して、前記金属酸化物微粒子を1重量部以上100重量部以下含有する請求項1乃至11のいずれかに記載のガスバリア性組成物。
- さらに溶媒を含む請求項1乃至12のいずれかに記載のガスバリア性組成物。
- (i)水酸基を有する水溶性高分子(A)およびカルボキシル基を有する水溶性高分子(B)の混合物、
および
(ii)水酸基とカルボキシル基とを有する水溶性高分子(AB)
の少なくとも一方を含む水溶性高分子(X)と、
金属アルコキシドおよび/またはその加水分解縮合物(C)と、
エステル化触媒(E)と、を混合する、ガスバリア性組成物の製造方法であって、
前記水溶性高分子(X)100重量部に対し、460重量部以上、2700重量部以下の量で前記(C)成分を添加し、0.01重量部以上、100重量部以下の量で前記(E)成分を添加することにより、前記水溶性高分子(X)と前記(C)成分と前記(E)成分とを混合する工程を含む、ガスバリア性組成物の製造方法。 - 水酸基を有する水溶性高分子(A)と、カルボキシル基を有する水溶性高分子(B)と、金属アルコキシドおよび/またはその加水分解縮合物(C)と、エステル化触媒(E)と、を混合する、ガスバリア性組成物の製造方法であって、
前記(A)成分と前記(B)成分との重量比が97/3から3/97となるように配合し、前記(A)成分と前記(B)成分との混合物100重量部に対し、460重量部以上、1600重量部以下の量で前記(C)成分を添加し、0.01重量部以上、100重量部以下の量で前記(E)成分を添加することにより、前記(A)成分と前記(B)成分と前記(C)成分と前記(E)成分とを混合する工程を含む、請求項14に記載のガスバリア性組成物の製造方法。 - 前記水溶性高分子(X)と前記(C)成分と前記(E)成分とを混合する前記工程は、
前記水溶性高分子(X)と、前記(E)成分および前記(C)成分とを混合する工程を含み、
前記水溶性高分子(X)と、前記(E)成分および前記(C)成分とを混合する前記工程において、前記(C)成分の加水分解縮合反応を進行させる、請求項14に記載のガスバリア性組成物の製造方法。 - 前記水溶性高分子(X)100重量部に対し、1分子中に金属酸化物と結合を形成できる官能基と、カルボキシル基と結合を形成できる官能基とをそれぞれ1つ以上有する化合物(D)を0.1重量部以上、20重量部以下の量となるように添加する工程をさらに含む、請求項14乃至16のいずれかに記載のガスバリア性組成物の製造方法。
- 請求項1乃至13のいずれかに記載のガスバリア性組成物の膜状物を形成し、これを熱処理するコーティング膜の製造方法。
- 請求項18に記載の方法により製造されたコーティング膜。
- 温度40℃、湿度90%の条件下で24時間放置した後の膜厚0.7μmのコーティング膜の酸素透過率が、30cc/m2・day・atm以下である請求項19に記載のコーティング膜。
- 請求項19または20に記載のコーティング膜を少なくとも1層含む積層体。
- 基板上に、前記コーティング膜を積層した請求項21に記載の積層体。
- 前記コーティング膜と、プラスチック基材とを積層した請求項21に記載の積層体。
- プラスチック基材と、前記プラスチック基材上に形成された無機化合物からなる蒸着膜と、前記蒸着膜上に形成された前記コーティング膜と、を備える請求項21に記載の積層体。
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JP2018126880A (ja) * | 2017-02-06 | 2018-08-16 | 大日本印刷株式会社 | ガスバリア積層体、及びガスバリア積層体の製造方法 |
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