WO2009125800A1 - ガスバリア性積層体およびその製造方法 - Google Patents
ガスバリア性積層体およびその製造方法 Download PDFInfo
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- WO2009125800A1 WO2009125800A1 PCT/JP2009/057225 JP2009057225W WO2009125800A1 WO 2009125800 A1 WO2009125800 A1 WO 2009125800A1 JP 2009057225 W JP2009057225 W JP 2009057225W WO 2009125800 A1 WO2009125800 A1 WO 2009125800A1
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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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- 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
- B32B27/10—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 paper or cardboard
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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
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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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
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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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
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/048—Forming gas barrier coatings
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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
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
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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
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
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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
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
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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
- B32B2255/00—Coating on the layer surface
- B32B2255/28—Multiple coating on one surface
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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
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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
- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
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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
- B32B2553/00—Packaging equipment or accessories not otherwise provided for
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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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
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
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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
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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
- Y10T428/31667—Next to addition polymer from unsaturated monomers, or aldehyde or ketone condensation product
Definitions
- the present invention relates to a gas barrier laminate and a method for producing the same.
- Gas packaging properties particularly oxygen barrier properties are often required for packaging materials for packaging foods and various articles. This is to prevent influences such as oxidative deterioration of the package contents due to oxygen or the like. Particularly in the packaging of foods, there is a problem that microorganisms propagate due to the presence of oxygen and the contents decay. For this reason, in the conventional packaging material, the gas barrier layer which prevents permeation
- a metal foil or a vapor deposition layer of a metal or a metal compound can be used.
- an aluminum foil, an aluminum vapor deposition layer, a silicon oxide vapor deposition layer, an aluminum oxide vapor deposition layer, or the like is used. in use.
- a metal layer such as an aluminum foil or an aluminum vapor-deposited layer has drawbacks such as invisible packaging contents and poor discardability.
- metal compound layers such as a silicon oxide vapor deposition layer and an aluminum oxide vapor deposition layer have a drawback that the gas barrier property is remarkably lowered due to deformation or dropping of the packaging material or impact during transportation.
- the gas barrier layer a layer made of a vinyl alcohol polymer having excellent gas barrier properties such as polyvinyl alcohol or ethylene-vinyl alcohol copolymer may be used. Since the layer made of these vinyl alcohol-based polymers is transparent and has the advantage that there are few problems in terms of disposal, the range of applications is expanding.
- the vinyl alcohol polymer is crystallized by hydrogen bonding between hydroxyl groups in the molecule, and exhibits gas barrier properties. For this reason, the conventional vinyl alcohol polymer exhibits high gas barrier properties in a dry state, but in a state of moisture absorption due to the influence of water vapor or the like, hydrogen bonds are loosened and gas barrier properties tend to be lowered. Therefore, it is difficult for a vinyl alcohol polymer such as polyvinyl alcohol to exhibit a high gas barrier property under high humidity.
- gas barrier materials materials containing hydrolyzed condensates of metal alkoxides (for example, tetramethoxysilane) and polymer compounds have been studied (for example, JP 2002-326303 A and JP 7-118543 A). Gazette, JP-A-2000-233478).
- metal alkoxides for example, tetramethoxysilane
- polymer compounds for example, JP 2002-326303 A and JP 7-118543 A. Gazette, JP-A-2000-233478).
- a gas barrier material a material composed of polyacrylic acid and a crosslinking component has been studied (for example, JP-A-2001-310425).
- a gas barrier layer made of a composition containing a hydrolysis condensate of a metal alkoxide and a polymer containing a —COO— group is immersed in a solution containing a divalent or higher metal ion. By this treatment, the —COO— group in the polymer is neutralized.
- the characteristics of the gas barrier layer can be dramatically improved.
- a packaging material used for a retort pouch needs to withstand treatment under severe conditions, and higher characteristics are required.
- the oxygen barrier property may be greatly lowered.
- transparency may be lowered.
- JP 2002-326303 A Japanese Patent Laid-Open No. 7-118543 JP 2000-233478 A JP 2001-310425 A WO2005 / 053954
- one of the objects of the present invention is to show a high oxygen barrier property even if the gas barrier layer is thin, and maintain a high oxygen barrier property and transparency even when retorting is performed under severe conditions, Furthermore, by providing a gas barrier laminate having excellent dimensional stability during processing such as printing and laminating and flexibility of the gas barrier laminate, and further having mechanical properties close to the mechanical properties inherent to the base film. is there.
- the present inventors have found that an excellent gas barrier layer can be obtained by using a specific composition.
- the present invention is based on this new finding.
- the gas barrier laminate of the present invention is a gas barrier laminate including a substrate and at least one gas barrier layer laminated on the substrate.
- the layer having gas barrier property includes a hydrolysis condensate of at least one compound (L) containing a hydrolyzable characteristic group, and at least one functional group selected from a carboxyl group and a carboxylic anhydride group. It consists of a composition containing the neutralized material of polymer (X) to contain.
- the compound (L) includes a compound (A) and a compound (B) containing Si to which a hydrolyzable characteristic group is bonded.
- the compound (A) is at least one compound represented by the following formula (I).
- M 1 X 1 m Y 1 nm (I) [In Formula (I), M 1 represents any one selected from Al, Ti, and Zr. X 1 represents any one selected from F, Cl, Br, I, OR 1 , R 2 COO, R 3 COCH 2 COR 4 , and NO 3 . Y 1 represents any one selected from F, Cl, Br, I, OR 5 , R 6 COO, R 7 COCH 2 COR 8 , NO 3 and R 9 . R 1 , R 2 , R 5 and R 6 each independently represents a hydrogen atom or an alkyl group. R 3 , R 4 , R 7 , R 8 and R 9 each independently represents an alkyl group. n is equal to the valence of M 1 . m represents an integer of 1 to n. ]
- the compound (B) includes at least one compound represented by the following formula (II). Si (OR 10 ) p R 11 4-pq X 2 q (II) [In the formula (II), R 10 represents an alkyl group. R 11 represents an alkyl group, an aralkyl group, an aryl group or an alkenyl group. X 2 represents a halogen atom. p and q each independently represents an integer of 0 to 4. 1 ⁇ p + q ⁇ 4. ]
- At least a part of the —COO— group contained in the functional group of the polymer (X) is neutralized with a divalent or higher valent metal ion.
- the proportion of the compound represented by the formula (II) in the compound (B) is 80 mol% or more.
- a ratio of [number of moles of the M 1 atom derived from the compound (A)] / [number of moles of Si atom derived from the compound (B)] is 0.1 / 99.9. 30. It is in the range of /70.0.
- the method of this invention for manufacturing a gas-barrier laminated body is the composition containing (i) hydrolysis condensate of the compound (L) containing the characteristic group which has hydrolyzability, and polymer (X). Forming a layer made of a material on a substrate, and (ii) bringing the layer into contact with a solution containing a metal ion having a valence of 2 or more.
- the compound (L) includes a compound (A) and a compound (B) containing Si to which a hydrolyzable characteristic group is bonded.
- the compound (A) is at least one compound represented by the following formula (I).
- M 1 X 1 m Y 1 nm (I) [In Formula (I), M 1 represents any one selected from Al, Ti, and Zr. X 1 represents any one selected from F, Cl, Br, I, OR 1 , R 2 COO, R 3 COCH 2 COR 4 , and NO 3 . Y 1 represents any one selected from F, Cl, Br, I, OR 5 , R 6 COO, R 7 COCH 2 COR 8 , NO 3 and R 9 . R 1 , R 2 , R 5 and R 6 each independently represents a hydrogen atom or an alkyl group. R 3 , R 4 , R 7 , R 8 and R 9 each independently represents an alkyl group. n is equal to the valence of M 1 . m represents an integer of 1 to n. ]
- the compound (B) includes at least one compound represented by the following formula (II). Si (OR 10 ) p R 11 4-pq X 2 q (II) [In the formula (II), R 10 represents an alkyl group. R 11 represents an alkyl group, an aralkyl group, an aryl group or an alkenyl group. X 2 represents a halogen atom. p and q each independently represents an integer of 0 to 4. 1 ⁇ p + q ⁇ 4. ]
- the polymer (X) is a polymer containing at least one functional group selected from a carboxyl group and a carboxylic anhydride group.
- the proportion of the compound represented by the formula (II) in the compound (B) is 80 mol% or more.
- a ratio of [number of moles of M 1 atom derived from the compound (A)] / [number of moles of Si atom derived from the compound (B)] is 0.1 / 99.9 to 30 It is in the range of 0.0 / 70.0.
- the gas barrier laminate produced by the production method of the present invention constitutes another aspect of the gas barrier laminate of the present invention.
- the gas barrier laminate of the present invention exhibits excellent oxygen barrier properties even when the gas barrier layer is thinned, retains excellent oxygen barrier properties even after retort treatment, and changes in appearance such as transparency are observed. In addition, these characteristics are maintained even when the retort conditions become severe. Moreover, since the gas barrier layer can be made thin in the gas barrier laminate of the present invention, the mechanical properties of the gas barrier laminate of the present invention approach those of the base film. Therefore, the gas barrier laminate of the present invention is excellent in mechanical properties such as flexibility and tensile strength and elongation, and is excellent in dimensional stability during processing such as printing and lamination.
- the gas barrier laminate of the present invention includes a substrate and at least one layer having gas barrier properties laminated on the substrate.
- the layer (hereinafter sometimes referred to as “gas barrier layer”) is made of a specific composition.
- the composition comprises a hydrolyzate condensate of at least one compound (L) containing a hydrolyzable characteristic group and at least one functional group selected from a carboxyl group and a carboxylic anhydride group. And a neutralized product of the combined (X).
- the compound (L) is at least one compound containing a hydrolyzable characteristic group, and is typically at least one compound containing a metal atom to which the hydrolyzable characteristic group is bonded. .
- the compound (L) includes a compound (A) and a compound (B) containing Si to which a hydrolyzable characteristic group is bonded.
- at least one functional group selected from a carboxyl group and a carboxylic anhydride group contained in the polymer (X) may be referred to as “functional group (F)”.
- At least a part of the —COO— group contained in the functional group (F) is neutralized with a divalent or higher metal ion.
- the —COO— group contained in the functional group (F) constitutes a salt with a divalent or higher valent metal ion.
- the gas barrier layer is laminated on at least one surface of the substrate.
- a gas barrier layer may be laminated
- the gas barrier laminate of the present invention may include layers other than the gas barrier layer.
- the gas barrier layer may be laminated
- the proportion of the hydrolyzed condensate of compound (L) and the neutralized product of polymer (X) in the composition is, for example, 50% by weight, 70% by weight, 80% by weight, 90% by weight, 95% by weight. % Or more, or 98% by weight or more.
- the composition which comprises a gas barrier layer contains the hydrolysis-condensation product of a compound (L).
- a compound (L) By hydrolyzing the compound (L), at least a part of the characteristic group of the compound (L) is substituted with a hydroxyl group. Furthermore, the hydrolyzate condenses to form a compound in which metal atoms are bonded through oxygen. When this condensation is repeated, a compound that can be substantially regarded as a metal oxide is formed.
- the compound (L) contains a hydrolyzable characteristic group (functional group). When those groups are not bonded, hydrolysis / condensation reaction does not occur or becomes extremely slow, and it is difficult to obtain the effects of the present invention.
- Si may be classified as a metalloid element, but in this specification, Si is described as a metal.
- the hydrolysis condensate can be produced from a specific raw material using, for example, a technique used in a known sol-gel method.
- the raw materials include compound (L), compound (L) partially hydrolyzed, compound (L) completely hydrolyzed, compound (L) partially hydrolyzed / condensed, A compound in which the compound (L) is completely hydrolyzed and partly condensed, or a combination thereof is used.
- These raw materials may be produced by a known method, or commercially available ones may be used.
- a condensate obtained by hydrolysis and condensation of about 2 to 10 molecules can be used as a raw material.
- a material obtained by hydrolyzing and condensing tetramethoxysilane into a dimer to 10-mer linear condensate can be used as a raw material.
- Compound (A) is at least one compound represented by the following formula (I).
- M 1 represents any one selected from Al, Ti, and Zr.
- X 1 represents any one selected from F, Cl, Br, I, OR 1 , R 2 COO, R 3 COCH 2 COR 4 , and NO 3 .
- Y 1 represents any one selected from F, Cl, Br, I, OR 5 , R 6 COO, R 7 COCH 2 COR 8 , NO 3 and R 9 .
- R 1 , R 2 , R 5 and R 6 each independently represents a hydrogen atom or an alkyl group.
- R 3 , R 4 , R 7 , R 8 and R 9 each independently represents an alkyl group.
- n is equal to the valence of M 1 .
- m represents an integer of 1 to n. ]
- X 1 and Y 1 may be the same or different.
- M 1 is preferably Al from the viewpoint of particularly reducing changes in appearance such as oxygen barrier properties and transparency before and after retorting of the obtained gas barrier laminate.
- X 1 is a group having hydrolyzability.
- X 1 is preferably any one selected from Cl, OR 1 , and NO 3 , and more preferably OR 1 .
- Y 1 is preferably any one selected from Cl, OR 5 , and NO 3 , and more preferably OR 5 .
- the carbon number of the alkyl group used for R 1 , R 2 , R 5 and R 6 is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, for example 1 or more and 4 or less.
- R 1 and R 5 are preferably a methyl group, an ethyl group, an iso-propyl group, an n-butyl group, or a t-butyl group, and particularly preferably an iso-propyl group or an n-butyl group.
- the number of carbon atoms of the alkyl group used for R 3 , R 4 , R 7 , R 8 and R 9 is preferably 1 or more and 4 or less, more preferably 1 or more and 2 or less.
- R 3 , R 4 , R 7 and R 8 are preferably a methyl group or an ethyl group.
- R 3 COCH 2 COR 4 and R 7 COCH 2 COR 8 are coordinated to atom M 1 at the carbonyl group.
- R 9 is preferably a methyl group or an ethyl group.
- [nm] may be 0 or 1, for example.
- the compound (A) include aluminum chloride, aluminum triethoxide, aluminum trinormal propoxide, aluminum triisopropoxide, aluminum trinormal butoxide, aluminum tri-t-butoxide, aluminum triacetate, aluminum acetylacetonate, nitric acid
- Aluminum compounds such as aluminum; titanium compounds such as titanium tetraisopropoxide, titanium tetranormal butoxide, titanium tetra (2-ethylhexoxide), titanium tetramethoxide, titanium acetylacetonate, titanium ethylacetoacetate; zirconium tetranormal Zirconium compounds such as propoxide, zirconium tetrabutoxide, zirconium tetraacetylacetonate and the like are included.
- Preferable examples of compound (A) include aluminum triisopropoxide and aluminum trinormal butoxide.
- the compound (B) is at least one Si compound containing Si to which a hydrolyzable characteristic group is bonded.
- the compound (B) includes at least one compound represented by the following formula (II).
- Si (OR 10 ) p R 11 4-pq X 2 q (II) [In the formula (II), R 10 represents an alkyl group. R 11 represents an alkyl group, an aralkyl group, an aryl group or an alkenyl group. X 2 represents a halogen atom. p and q each independently represents an integer of 0 to 4. 1 ⁇ p + q ⁇ 4. ]
- Examples of the alkyl group represented by R 10 include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, and a t-butyl group, and a methyl group or an ethyl group is preferable.
- Examples of the halogen atom represented by X 2 include a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable.
- Examples of the alkyl group represented by R 11 include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a t-butyl group, and an n-octyl group.
- examples of the aralkyl group For example, benzyl group, phenethyl group, trityl group and the like can be mentioned.
- examples of the aryl group represented by R 11 include a phenyl group, a naphthyl group, a tolyl group, a xylyl group, and a mesityl group.
- Examples of the alkenyl group include a vinyl group and an allyl group.
- Specific examples of the compound (B) represented by the formula (II) include tetrachlorosilane, tetrabromosilane, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, octyltrimethoxysilane, phenyltri Methoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, chlorotrimethoxysilane, chlorotriethoxysilane, dichlorodimethoxysilane, dichlorodiethoxysilane, trichloromethoxysilane, trichloroethoxysilane, and vinyltrichlorosilane are included.
- Preferred examples of the compound (B) represented by the formula (II) include tetramethoxysilane and tetraethoxysilane.
- Compound (B) may further contain at least one compound represented by the following formula (III) in addition to the compound represented by formula (II).
- formula (III) changes in oxygen barrier properties and changes in appearance such as transparency before and after the boil treatment and before and after the retort treatment are further reduced.
- R 12 represents an alkyl group.
- X 3 represents a halogen atom.
- Z 3 represents an alkyl group substituted with a functional group having reactivity with a carboxyl group.
- r and s each independently represents an integer of 0 to 3. 1 ⁇ r + s ⁇ 3. ]
- Examples of the alkyl group represented by R 12 include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, and a t-butyl group, and a methyl group or an ethyl group is preferable.
- Examples of the halogen atom represented by X 3 include a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable.
- Examples of the functional group having reactivity with a carboxyl group that Z 3 has include an epoxy group, an amino group, a hydroxyl group, a halogen atom, a mercapto group, an isocyanate group, a ureido group, an oxazoline group, and a carbodiimide group.
- an epoxy group, an amino group, an isocyanate group, a ureido group, or a halogen atom is present from the viewpoint of particularly reducing changes in appearance such as oxygen barrier properties and transparency before and after retorting of the obtained gas barrier laminate.
- at least one selected from an epoxy group, an amino group, and an isocyanate group may be used.
- Examples of the alkyl group substituted with such a functional group include those exemplified for R 12 .
- Specific examples of the compound represented by the formula (III) include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropyltrichlorosilane, ⁇ -aminopropyltrisilane.
- isocyanate propyl triethoxysilane .gamma. isocyanate propyl trichlorosilane, .gamma.-ureidopropyltrimethoxysilane, .gamma.-ureidopropyltriethoxysilane include .gamma. ureidopropyltrimethoxysilane trichlorosilane.
- Preferred examples of the compound represented by the formula (III) include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -chloropropyltrimethoxysilane, and ⁇ -chloropropyltriethoxysilane. , ⁇ -aminopropyltrimethoxysilane, and ⁇ -aminopropyltriethoxysilane.
- the inventors have obtained a gas barrier laminate obtained by using a hydrolysis condensate of the compound (L) containing the compound (A) and the compound (B), which has excellent gas barrier properties, boil resistance, It has been found that it exhibits hot water resistance such as retort resistance. That is, it was found that the gas barrier laminate of the present invention not only has excellent gas barrier properties but also maintains excellent gas barrier properties even after being subjected to boil treatment or retort treatment, and there is no change in appearance. Surprisingly, in the gas barrier laminate, as described above, when the gas barrier layer is thinned, the gas barrier property may be greatly reduced. However, by using the hydrolysis condensate of the compound (L), It has been newly found that even if the gas barrier layer is thinned, a high gas barrier property is maintained.
- the ratio of [number of moles of M 1 atom derived from compound (A)] / [number of moles of Si atom derived from compound (B)] is preferably Is in the range of 1.2 / 98.8 to 30.0 / 70.0, more preferably in the range of 1.9 / 98.1 to 30.0 / 70.0, and even more preferably 2.8. /97.2 to 30.0 / 70.0.
- the ratio is in the range of 0.5 / 99.5 to 30.0 / 70.0, in the range of 1.5 / 98.5 to 20.0 / 80.0, or 2.5 / 97.5 to 10 It may be in the range of 0.0 / 90.0.
- the present inventors use, in addition to the compound represented by the compound (A) and the formula (II), a hydrolysis condensate of the compound (L) further comprising a compound represented by the formula (III), It has been found that the gas barrier laminate exhibits further excellent gas barrier properties and hot water resistance such as boil resistance and retort resistance.
- the ratio of [number of moles of Si derived from the compound represented by formula (II)] / [number of moles of Si derived from the compound represented by formula (III)] was 99.5 / 0.5 to It is preferably in the range of 80.0 / 20.0. If this ratio is greater than 99.5 / 0.5, the resulting gas barrier laminate has properties that do not change its appearance such as gas barrier properties and transparency before and after boiling and retorting, that is, hot water resistance decreases. There is a case. Moreover, when this ratio is smaller than 80/20, the gas barrier property of the gas barrier laminate obtained may deteriorate. This ratio is more preferably in the range of 98.0 / 2.0 to 89.9 / 10.1 from the viewpoint of improving the hot water resistance and gas barrier properties of the gas barrier laminate.
- the total ratio of the compound (A) and the compound (B) in the compound (L) is, for example, 80 mol% or more and 100 mol% or less, and 90 mol% or more, 95 mol% or more, 95 mol% or more, 98 The mol% or more, 99 mol% or more, or 100 mol% may be sufficient.
- the proportion of the compound represented by the formula (II) in the compound (B) is 80 mol% or more and 100 mol% or less, for example, 90 mol% or more, 95 mol% or more. 98 mol% or more, or 100 mol%.
- the compound (B) consists only of the compound represented by the formula (II), and in another example, the compound (B) is represented by the compound represented by the formula (II) and the formula (III). It consists only of a compound.
- the number of molecules condensed in the hydrolyzed condensate of compound (L) can be controlled by the conditions at the time of hydrolysis / condensation.
- the number of molecules to be condensed can be controlled by the amount of water, the type and concentration of the catalyst, the temperature at which hydrolysis condensation is performed, and the like.
- the ratio of the sum to the weight of the organic component derived from the polymer (X) is preferably in the range of 20.0 / 80.0 to 80.0 / 20.0, 30.5 / 69.5 to More preferably, it is in the range of 70/30.
- the weight of the inorganic component derived from the compound (L) can be calculated from the weight of the raw material used when preparing the composition. That is, compound (L), compound (L) partially hydrolyzed, compound (L) completely hydrolyzed, compound (L) partially hydrolyzed, compound (L) Assuming that the product is completely hydrolyzed and partly condensed, or a combination of these, is completely hydrolyzed and condensed into a metal oxide, and the weight of the metal oxide is calculated as compound (L). It is regarded as the weight of the inorganic component derived from.
- the composition formula is This is a compound represented by M 1 On / 2 .
- the compound (A) represented by the formula (I) contains R 9 , when it is completely hydrolyzed / condensed, the compound represented by the formula M 1 O m / 2 R 9 nm It becomes.
- the M 1 O m / 2 portion is a metal oxide.
- R 9 is an organic component derived from the compound (L).
- it calculates similarly about a compound (B).
- R 11 and Z 3 are organic components derived from the compound (L).
- the value obtained by dividing the weight of the metal oxide by the weight of the active ingredient added until the end of the step (i) described later and multiplying the value by 100 is the content (%) of the hydrolysis condensate in this specification. It is.
- the weight of the active ingredient refers to a compound or solvent generated in the process in which the above-described compound (L) is converted into a metal oxide from the weight of all the ingredients added until the end of the step (i) described later. This is the weight excluding the weight of volatile components.
- the weight of the ions is also the weight of the organic component derived from the polymer (X). Added to.
- the composition constituting the gas barrier layer includes a neutralized product of a polymer containing at least one functional group selected from a carboxyl group and a carboxylic anhydride group.
- the polymer may be referred to as “carboxylic acid-containing polymer”.
- the neutralized product of the carboxylic acid-containing polymer can be obtained by neutralizing at least part of the —COO— group contained in the functional group of the carboxylic acid-containing polymer with a divalent or higher metal ion.
- the carboxylic acid-containing polymer has two or more carboxyl groups or one or more carboxylic anhydride groups in one polymer molecule.
- a polymer containing two or more structural units having one or more carboxyl groups such as an acrylic acid unit, a methacrylic acid unit, a maleic acid unit, and an itaconic acid unit in one molecule of the polymer is used. it can.
- the polymer containing the structural unit which has the structure of carboxylic anhydrides such as a maleic anhydride unit and a phthalic anhydride unit, can also be used.
- One type or two types of structural units having one or more carboxyl groups and / or structural units having a structure of carboxylic anhydride hereinafter, these may be collectively referred to as “carboxylic acid-containing units (G)”. The above may be contained in the carboxylic acid-containing polymer.
- the content of the carboxylic acid-containing unit (G) in all the structural units of the carboxylic acid-containing polymer is set to 10 mol% or more.
- the content is more preferably 20 mol% or more, further preferably 40 mol% or more, and particularly preferably 70 mol% or more.
- a carboxylic acid containing polymer contains both the structural unit which contains 1 or more of carboxyl groups, and the structural unit which has a structure of a carboxylic anhydride, the total of both should just be said range.
- Other structural units other than the carboxylic acid-containing unit (G) that may be contained in the carboxylic acid-containing polymer are not particularly limited, but are methyl acrylate units, methyl methacrylate units, ethyl acrylate units, methacrylic acid.
- Structural units derived from (meth) acrylic esters such as ethyl units, butyl acrylate units and butyl methacrylate units; structural units derived from vinyl esters such as vinyl formate units and vinyl acetate units; styrene units, One or more structural units selected from p-styrene sulfonic acid units; structural units derived from olefins such as ethylene units, propylene units, and isobutylene units.
- the carboxylic acid-containing polymer contains two or more structural units
- the carboxylic acid-containing polymer is in the form of an alternating copolymer, a random copolymer, a block copolymer, or a taper. It may be in the form of a type copolymer.
- carboxylic acid-containing polymer examples include polyacrylic acid, polymethacrylic acid, and poly (acrylic acid / methacrylic acid).
- the carboxylic acid-containing polymer may be at least one polymer selected from polyacrylic acid and polymethacrylic acid.
- Specific examples of the case of containing other structural units other than the carboxylic acid-containing unit (G) include ethylene-maleic anhydride copolymers, styrene-maleic anhydride copolymers, isobutylene-maleic anhydride. Examples include alternating copolymers, ethylene-acrylic acid copolymers, and saponified ethylene-ethyl acrylate copolymers.
- the molecular weight of the carboxylic acid-containing polymer is not particularly limited, but the number average molecular weight is 5,000 or more from the viewpoint of excellent gas barrier properties of the resulting gas barrier laminate and excellent mechanical properties such as drop impact strength. Preferably, it is preferably 10,000 or more, and more preferably 20,000 or more.
- the upper limit of the number average molecular weight of the carboxylic acid-containing polymer is not particularly limited, but is generally 1,500,000 or less.
- the molecular weight distribution of the carboxylic acid-containing polymer is not particularly limited, from the viewpoint of improving the surface appearance such as haze of the gas barrier laminate and the storage stability of the solution (U) described later,
- the molecular weight distribution represented by the ratio of weight average molecular weight / number average molecular weight of the carboxylic acid-containing polymer is preferably in the range of 1 to 6, more preferably in the range of 1 to 5, and in the range of 1 to 4. More preferably.
- the neutralized product of the carboxylic acid-containing polymer is a divalent or higher-valent metal having at least a part of at least one functional group (functional group (F)) selected from the carboxyl group and carboxylic anhydride group of the carboxylic acid-containing polymer. Obtained by neutralization with ions. In other words, this polymer contains a carboxyl group neutralized with a divalent or higher metal ion.
- the metal ion neutralizing the functional group (F) is divalent or higher.
- the functional group (F) is not neutralized or neutralized only by monovalent ions, a laminate having good gas barrier properties cannot be obtained.
- divalent or higher metal ions include calcium ions, magnesium ions, divalent iron ions, trivalent iron ions, zinc ions, divalent copper ions, lead ions, divalent mercury ions, barium ions, A nickel ion, a zirconium ion, an aluminum ion, a titanium ion, etc. can be mentioned.
- the divalent or higher valent metal ion may be at least one ion selected from the group consisting of calcium ion, magnesium ion, barium ion, zinc ion, iron ion and aluminum ion.
- the —COO— group contained in the functional group (F) of the carboxylic acid-containing polymer is neutralized with, for example, 10 mol% or more (for example, 15 mol% or more) with a divalent metal ion or more.
- the gas barrier laminate of the present invention exhibits good gas barrier properties.
- the carboxylic anhydride group is considered to contain two —COO— groups. That is, when there are a moles of carboxyl groups and b moles of carboxylic acid anhydride groups, the total —COO— groups contained are (a + 2b) moles.
- the proportion of the —COO— group contained in the functional group (F) is neutralized with a divalent or higher metal ion is preferably 60 mol% or more and 100 mol% or less, more preferably 70 mol% or more. More preferably, it is 80 mol% or more. By increasing the proportion of neutralization, higher gas barrier properties can be realized.
- the degree of neutralization (ionization degree) of the functional group (F) is determined by measuring the infrared absorption spectrum of the gas barrier laminate by the ATR method (total reflection measurement method) or scraping the gas barrier layer from the gas barrier laminate,
- the infrared absorption spectrum can be obtained by measuring by the KBr method. It can also be obtained from the value of the fluorescent X-ray intensity of the metal element used for ionization by fluorescent X-ray measurement.
- the ionization degree of the polymer (X) constituting the gas barrier layer laminated on the substrate not containing an ester bond is measured by an infrared absorption spectrum.
- the fluorescence X-ray intensity of the metal element used for ionization is determined by fluorescent X-ray measurement for the laminate in which the degree of ionization is measured.
- the same measurement is implemented about the laminated body from which only an ionization degree differs.
- a correlation between the degree of ionization and the fluorescent X-ray intensity of the metal element used for ionization is obtained, and a calibration curve is created.
- the composition constituting the gas barrier layer of the present invention may contain a compound (P) containing two or more amino groups.
- Compound (P) is a compound different from compound (L) and polymer (X).
- the compound (P) is further included, at least a part of the —COO— group contained in the functional group (F) of the polymer (X) is neutralized and / or reacted with the compound (P); Become.
- alkylene diamines, polyalkylene polyamines, alicyclic polyamines, aromatic polyamines, polyvinylamines, and the like can be used, but the gas barrier property of the gas barrier laminate is improved. Therefore, alkylene diamine is preferable.
- the compound (P) include hydrazine, ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, diaminodiphenylmethane, 1,3-diaminocyclohexane, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane. , Xylylenediamine, chitosan, polyallylamine, polyvinylamine and the like. From the viewpoint of improving the gas barrier properties of the gas barrier laminate, ethylenediamine, propylenediamine, and chitosan are preferable.
- the molar ratio of [amino group contained in compound (P)] / [-COO-group contained in functional group of carboxylic acid-containing polymer] is the viewpoint that the hot water resistance of the gas barrier laminate of the present invention becomes better. Therefore, it is preferably in the range of 0.2 / 100 to 20/100, more preferably in the range of 0.5 / 100 to 15/100, and in the range of 1/100 to 10/100. Particularly preferred.
- the compound (P) When the compound (P) is added to the carboxylic acid-containing polymer, the compound (P) may be previously neutralized with an acid.
- the acid used for neutralization include hydrochloric acid, nitric acid, sulfuric acid, acetic acid, and carbonic acid. From the viewpoint of better gas barrier properties of the resulting gas barrier laminate, it is preferable to use hydrochloric acid, acetic acid, and carbonic acid.
- the composition constituting the gas barrier layer of the present invention may contain a compound (Q) containing two or more hydroxyl groups.
- the compound (Q) is further included, at least part of the —COO— group contained in the functional group (F) of the polymer (X) is reacted with the compound (Q) to form an ester bond. It becomes.
- the gas barrier property after elongation of the gas barrier laminate is improved. More specifically, by adding the compound (Q), the gas barrier layer is hardly damaged even when the gas barrier laminate is elongated. As a result, high gas barrier properties are maintained even after being stretched. For example, the gas barrier property of the gas barrier laminate is hardly lowered even in a state after elongation due to tension during processing such as printing or laminating or elongation when a bag filled with food is dropped.
- Compound (Q) is a compound different from compound (L) and polymer (X).
- the compound (Q) includes a low molecular weight compound and a high molecular weight compound.
- Preferred examples of the compound (Q) include polyvinyl alcohol, partially saponified polyvinyl acetate, ethylene-vinyl alcohol copolymer, polyethylene glycol, polyhydroxyethyl (meth) acrylate, polysaccharides such as starch, starch and other polysaccharides. Polymer compounds such as polysaccharide derivatives derived from saccharides are included.
- composition constituting the gas barrier layer may be carbonate, hydrochloride, nitrate, hydrogen carbonate, sulfate, hydrogen sulfate, phosphate, boric acid within the range not impairing the effects of the present invention.
- Salts inorganic acid metal salts such as aluminate; organic acid metal salts such as oxalate, acetate, tartrate, stearate; acetylacetonate metal complexes such as aluminum acetylacetonate, titanocene, etc.
- Metal complexes such as cyclopentadienyl metal complexes and cyano metal complexes; layered clay compounds, crosslinking agents, plasticizers, antioxidants, ultraviolet absorbers, flame retardants and the like may be contained.
- the composition constituting the gas barrier layer may contain a metal oxide fine powder, a silica fine powder, and the like.
- base materials made of various materials can be used.
- a film having a predetermined shape made of a film such as a thermoplastic resin film or a thermosetting resin film; a fiber assembly such as fabric or paper; wood; a metal oxide or a metal can be used.
- a thermoplastic resin film is especially useful as a base material of the gas-barrier laminated body used for food packaging materials.
- the substrate may also include a paper layer.
- thermoplastic resin film examples include polyolefin resins such as polyethylene and polypropylene; polyester resins such as polyethylene terephthalate, polyethylene-2,6-naphthalate, polybutylene terephthalate and copolymers thereof; nylon-6, nylon- 66, polyamide resin such as nylon-12; polystyrene, poly (meth) acrylate, polyacrylonitrile, polyvinyl acetate, polycarbonate, polyarylate, regenerated cellulose, polyimide, polyetherimide, polysulfone, polyethersulfone, poly Examples thereof include films obtained by molding ether ether ketone, ionomer resin and the like.
- a film made of polyethylene, polypropylene, polyethylene terephthalate, nylon-6, or nylon-66 is preferable.
- the thermoplastic resin film may be a stretched film or an unstretched film. However, since the processability of the gas barrier laminate of the present invention, such as printing and laminating, is excellent, it is a stretched film, particularly biaxially stretched. A film is preferred.
- the biaxially stretched film may be a biaxially stretched film produced by any of the simultaneous biaxial stretching method, the sequential biaxial stretching method, and the tubular stretching method.
- the gas barrier laminate of the present invention may further include an adhesive layer (H) disposed between the base material and the gas barrier layer.
- an adhesive layer (H) made of an adhesive resin can be formed by treating the surface of the substrate with a known anchor coating agent or applying a known adhesive to the surface of the substrate.
- an adhesive resin containing a urethane bond and having a nitrogen atom (a nitrogen atom of the urethane bond) occupying the entire resin is in the range of 0.5 to 12% by weight. It was found. By using such an adhesive resin, the adhesion between the substrate and the gas barrier layer can be particularly enhanced.
- the content of nitrogen atoms (urethane bond nitrogen atoms) contained in the adhesive resin is more preferably in the range of 2 to 11% by weight, and still more preferably in the range of 3 to 8% by weight.
- the adhesive resin containing a urethane bond a two-component reactive polyretane-based adhesive in which a polyisocyanate component and a polyol component are mixed and reacted is preferable.
- the strength of the gas barrier laminate can be increased by increasing the thickness of the adhesive layer (H).
- the thickness of the adhesive layer (H) is preferably in the range of 0.03 ⁇ m to 0.18 ⁇ m. According to this configuration, when processing such as printing or laminating is performed on the gas barrier laminate of the present invention, deterioration of gas barrier properties and appearance can be suppressed, and further, the gas barrier laminate of the present invention is used. It is possible to increase the drop strength of the packaging material.
- the thickness of the adhesive layer (H) is more preferably in the range of 0.04 ⁇ m to 0.14 ⁇ m, and still more preferably in the range of 0.05 ⁇ m to 0.10 ⁇ m.
- the total thickness of the gas barrier layers contained in the laminate is preferably 1.0 ⁇ m or less, for example 0.9 ⁇ m or less.
- the dimensional change of the gas barrier laminate of the present invention during processing such as printing and laminating can be kept low, and the flexibility of the gas barrier laminate of the present invention is increased.
- the characteristics can be brought close to the mechanical characteristics of the film itself used for the substrate.
- the thickness of one gas barrier layer is preferably 0.05 ⁇ m or more (for example, 0.15 ⁇ m or more) from the viewpoint of improving the gas barrier properties of the gas barrier laminate of the present invention. Further, the total thickness of the gas barrier layer is more preferably 0.1 ⁇ m or more (for example, 0.2 ⁇ m or more). The thickness of the gas barrier layer can be controlled by the concentration of the solution used for forming the gas barrier layer and the coating method.
- the laminate of the present invention may include a layer made of an inorganic material (hereinafter sometimes referred to as “inorganic layer”) between the base material and the gas barrier layer.
- the inorganic layer can be formed of an inorganic material such as an inorganic oxide.
- the inorganic layer can be formed by a vapor deposition method such as a vapor deposition method.
- the inorganic substance constituting the inorganic layer is not particularly limited as long as it has a gas barrier property against oxygen, water vapor, and the like, and preferably has transparency.
- the inorganic layer can be formed using an inorganic oxide such as aluminum oxide, silicon oxide, silicon oxynitride, magnesium oxide, tin oxide, or a mixture thereof.
- aluminum oxide, silicon oxide, and magnesium oxide can be preferably used from the viewpoint of excellent barrier properties against gases such as oxygen and water vapor.
- the preferred thickness of the inorganic layer varies depending on the type of inorganic oxide constituting the inorganic layer, but is usually in the range of 2 nm to 500 nm. Within this range, a thickness that provides good gas barrier properties and mechanical properties of the gas barrier laminate may be selected. When the thickness of the inorganic layer is less than 2 nm, the expression of the barrier property of the inorganic layer with respect to a gas such as oxygen or water vapor is not reproducible, and the inorganic layer may not exhibit a sufficient gas barrier property. When the thickness of the inorganic layer exceeds 500 nm, the gas barrier property of the inorganic layer tends to be lowered when the gas barrier laminate is pulled or bent.
- the thickness of the inorganic layer is preferably in the range of 5 nm to 200 nm, more preferably in the range of 10 nm to 100 nm.
- the inorganic layer can be formed by depositing an inorganic oxide on the substrate.
- the forming method include a vacuum deposition method, a sputtering method, an ion plating method, a chemical vapor deposition method (CVD), and the like.
- the vacuum evaporation method is preferably used from the viewpoint of productivity.
- a heating method in performing vacuum deposition any of an electron beam heating method, a resistance heating method, and an induction heating method is preferable.
- the fine structure of the gas barrier layer is not particularly limited. However, when the gas barrier layer has the fine structure described below, it is preferable because a decrease in gas barrier properties when the gas barrier laminate is stretched can be suppressed.
- a preferable fine structure is a sea-island structure composed of a sea phase ( ⁇ ) and an island phase ( ⁇ ).
- the island phase ( ⁇ ) is a region where the ratio of the hydrolysis condensate of the compound (L) is higher than that of the sea phase ( ⁇ ).
- the sea phase ( ⁇ ) and the island phase ( ⁇ ) each further have a fine structure.
- the sea phase ( ⁇ ) is composed of a sea phase ( ⁇ 1) mainly composed of a neutralized product of a carboxylic acid-containing polymer and an island phase ( ⁇ 2) mainly composed of a hydrolysis condensate of the compound (L).
- the sea island structure to be formed may be further formed.
- the island phase ( ⁇ ) is composed of a sea phase ( ⁇ 1) mainly composed of a neutralized product of a carboxylic acid-containing polymer and an island phase ( ⁇ 2) mainly composed of a hydrolysis condensate of the compound (L).
- the sea island structure to be formed may be further formed.
- the ratio (volume ratio) of [island phase ( ⁇ 2) / sea phase ( ⁇ 1)] in the island phase ( ⁇ ) is the ratio of [island phase ( ⁇ 2) / sea phase ( ⁇ 1)] in the sea phase ( ⁇ ). Is preferably larger.
- the diameter of the island phase ( ⁇ ) is preferably in the range of 30 nm to 1200 nm, more preferably in the range of 50 to 500 nm, and still more preferably in the range of 50 nm to 400 nm.
- the diameter of the island phase ( ⁇ 2) and the island phase ( ⁇ 2) is preferably 50 nm or less, more preferably 30 nm or less, and even more preferably 20 nm or less.
- an appropriate hydrolysis condensation of the compound (L) occurs in preference to the crosslinking reaction between the compound (L) and the carboxylic acid-containing polymer.
- the specific compound (L) is used in an appropriate ratio with the carboxylic acid-containing polymer, and the compound (L) is preliminarily hydrolyzed and condensed before mixing with the carboxylic acid-containing polymer.
- a method such as using a condensation catalyst can be employed.
- the layer of the hydrolytic condensate of compound (L) formed on the surface of the gas barrier layer may be referred to as “skin layer”.
- skin layer By forming the skin layer, the water resistance of the gas barrier layer surface is improved.
- the skin layer made of the hydrolyzed condensate of compound (L) has a characteristic that the hydrophobic property is imparted to the surface of the gas barrier layer, and the gas barrier layer does not stick even when the gas barrier layers wet with water are stacked. To grant.
- the present inventors have found that there is a correlation between the contact angle between the gas barrier layer and water and the preferred skin layer, and the preferred skin layer is formed when the contact angle satisfies the following conditions. I found out. When the contact angle between the gas barrier layer and water is less than 20 °, the skin layer may not be sufficiently formed.
- the surface of the gas barrier layer easily swells with water, and if the laminates are stacked in a wet state, they may rarely stick together.
- the contact angle is 20 ° or more, the skin layer is sufficiently formed, and the surface of the gas barrier layer does not swell with water, so that no sticking occurs.
- the contact angle between the gas barrier layer and water is preferably 24 ° or more, and more preferably 26 ° or more.
- the contact angle is preferably 65 ° or less, more preferably 60 ° or less, and still more preferably 58 ° or less.
- the gas barrier laminate of the present invention may contain other layers (for example, a thermoplastic resin film or paper) in addition to the base material and the gas barrier layer. By adding such other layers, it is possible to impart heat sealability to the gas barrier laminate or to improve the mechanical properties of the gas barrier laminate.
- other layers for example, a thermoplastic resin film or paper
- gas barrier laminate of the present invention when a thermoplastic resin film or paper (layer) is used for the substrate are shown below.
- film (layer) in order to simplify the description, the notation of “film (layer)” may be omitted and only the material may be described.
- Examples of the configuration of the gas barrier laminate of the present invention include the following configurations. (1) Gas barrier layer / polyester / polyamide / polyolefin, (2) Gas barrier layer / polyester / gas barrier layer / polyamide / polyolefin, (3) polyester / gas barrier layer / polyamide / polyolefin, (4) Gas barrier layer / polyamide / polyester / polyolefin, (5) Gas barrier layer / polyamide / gas barrier layer / polyester / polyolefin, (6) Polyamide / Gas barrier layer / Polyester / Polyolefin, (7) Gas barrier layer / polyolefin / polyamide / polyolefin, (8) Gas barrier layer / polyolefin / gas barrier layer / polyamide / polyolefin, (9) Polyolefin / Gas barrier layer / Polyamide / Polyolefin, (10) Gas barrier layer / polyolefin / polyolefin, (11) Gas barrier layer / polyolef
- the polyolefin is preferably polypropylene or polyethylene
- the polyester is preferably polyethylene terephthalate (PET)
- the polyamide is preferably nylon-6.
- the hydroxyl group-containing polymer is preferably an ethylene-vinyl alcohol copolymer.
- a package can be obtained using the gas barrier laminate of the present invention.
- This package can be applied to various applications, and is preferably used for applications that require a gas barrier such as oxygen gas.
- a package using the gas barrier laminate of the present invention is preferably used as a package for retort food.
- a paper container can be obtained by using the base material containing a paper layer.
- the production method of the present invention includes steps (i) and (ii).
- Step (i) is a step of forming, on a substrate, a layer made of a composition containing a hydrolysis condensate of compound (L) containing a hydrolyzable characteristic group and polymer (X). .
- the layer is formed directly on the substrate or is formed on the substrate via another layer.
- Compound (L) includes compound (A) and compound (B). It should be noted that the reactivity of hydrolysis and condensation of the compound (L) can be controlled by adding the compound (D) having a carboxyl group-containing molecular weight of 100 or less to the compound (L). The gas barrier property and hot water resistance of the body are good. Details of the compound (D) will be described later.
- the compound (A), the compound (B), and the ratio of these compounds are the same as those described for the composition constituting the gas barrier layer.
- the next step (ii) is a step of bringing the layer formed in step (i) into contact with a solution containing divalent or higher metal ions (hereinafter, this step may be referred to as an ionization step). For example, it can be performed by spraying a solution containing divalent or higher metal ions on the formed layer, or immersing both the base material and the layer on the base material in a solution containing divalent or higher metal ions. .
- the step (ii) at least a part of the —COO— group contained in the functional group (F) of the polymer (X) is neutralized.
- step (i) when the compound (L) which is not hydrolytically condensed and a carboxylic acid containing polymer are mixed, both may react and it may become difficult to apply
- step (i) (Ia) A solution comprising at least one compound selected from the compound (A) and a partial hydrolysis-condensation product of the compound (A), and a compound (D) containing a carboxyl group and having a molecular weight of 100 or less Preparing (S); (Ib) preparing a solution (T) by mixing at least one compound selected from the compound (B) and a partial hydrolysis condensate of the compound (B) with the solution (S); (Ic) forming a hydrolysis condensate (oligomer (V)) of a plurality of compounds (L) containing the compound (A) and the compound (B) in the solution (T); (Id) preparing a solution (U) by mixing the solution (T) having undergone the step (ic) and the polymer (X); And (ie) forming a layer by applying the solution (U) to a substrate and drying it.
- S Preparing
- the oligomer (V) obtained by hydrolyzing and condensing the compound (L) includes a compound (L) partially hydrolyzed, a compound (L) completely hydrolyzed, a compound (L ) Is partially hydrolyzed and condensed, and compound (L) is at least one metal element-containing compound selected from completely hydrolyzed and partially condensed.
- compound (L) -based component such a metal element-containing compound may be referred to as “compound (L) -based component”.
- the step (ia), the step (ib), the step (ic), the step (id), and the step (ie) will be described more specifically.
- Step (ia) is a step of hydrolyzing and condensing the compound (A) constituting the compound (L) under specific conditions. It is preferable to hydrolyze and condense the compound (A) in a reaction system containing the compound (A), an acid catalyst, water and, if necessary, an organic solvent. Specifically, a technique used in a known sol-gel method can be applied. When hydrolyzing and condensing, it is extremely important to add a compound (D) containing a carboxyl group and having a molecular weight of 100 or less (hereinafter sometimes simply referred to as compound (D)) in order to control the reaction. Preferably, by adding the compound (D), gelation can be suppressed in the step of hydrolyzing and condensing the compound (A).
- Compound (D) is compound (A), compound (A) partially hydrolyzed, compound (A) completely hydrolyzed, compound (A) partially hydrolyzed and condensed, And a metal element-containing compound containing at least one compound selected from those in which the compound (A) is completely hydrolyzed and partially condensed (hereinafter, this metal element-containing compound is referred to as “compound (A) component”). And the compound (D) acts on the compound (A) system component, the above-mentioned effect is exhibited.
- the method for adding the compound (D) is not particularly limited as long as the compound (A) is added before the component of the compound (A) is gelled by the hydrolysis condensation reaction. be able to.
- the ratio of the number of moles] is preferably in the range of 0.25 / 1 to 30/1, more preferably in the range of 0.5 / 1 to 20/1, and 0.75 / 1 to 10/10. More preferably, it is in the range of / 1.
- Compound (D) is not particularly limited as long as it is a compound containing a carboxyl group and having a molecular weight of 100 or less. From the viewpoint of increasing the reaction rate between the compound (A) and the functional group (F) of the polymer (X) and improving the hot water resistance and gas barrier properties of the gas barrier laminate of the present invention, acetic acid is used as the compound (D). , Propionic acid, hexanoic acid and the like, and acetic acid is most preferable.
- a solution (T) is prepared. Specifically, for example, a solution (S) and an organic solvent as necessary are added to the compound (B) which is a constituent component of the compound (L), and then an acid catalyst, water and an organic solvent as needed are added.
- the solution (T) can be prepared by the method of adding.
- step (ic) hydrolysis and condensation are performed in a reaction system containing, for example, compound (A) component, compound (B), acid catalyst, water, and if necessary an organic solvent.
- a technique used in a known sol-gel method can be applied to this technique.
- compound (A) system component, compound (B), compound (B) partially hydrolyzed, compound (B) completely hydrolyzed, compound (B) partially hydrolyzed A solution of the metal element-containing compound containing at least one selected from the condensed product and the compound (B) which is completely hydrolyzed and partially condensed can be obtained.
- a known acid can be used as the acid catalyst used in step (ia) and step (ib).
- a known acid can be used.
- hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, benzoic acid, acetic acid, lactic acid, Butyric acid, carbonic acid, oxalic acid, maleic acid and the like can be used.
- hydrochloric acid, sulfuric acid, nitric acid, acetic acid, lactic acid and butyric acid are particularly preferred.
- Preferred amount of acid catalyst may vary depending on the type of acid used, the metal atom to 1 mol of the compound (L), is preferably in the range of 1 ⁇ 10 -5 ⁇ 10 mol, 1 ⁇ 10 - It is more preferably in the range of 4 to 5 mol, and further preferably in the range of 5 ⁇ 10 ⁇ 4 to 1 mol.
- the amount of the acid catalyst used is within this range, a gas barrier laminate having a high gas barrier property can be obtained.
- the amount of water used in step (ia) and step (ib) varies depending on the type of compound (L), but relative to 1 equivalent of the characteristic group having hydrolyzability of compound (L). , Preferably in the range of 0.05 to 10 equivalents, more preferably in the range of 0.1 to 5 equivalents, and still more preferably in the range of 0.2 to 3 equivalents. When the amount of water used is in this range, the gas barrier property of the resulting gas barrier laminate is particularly excellent.
- a component containing water such as hydrochloric acid
- the amount of water used is also taken into account the amount of water introduced by the component. Is preferably determined.
- an organic solvent may be used as necessary.
- the organic solvent used will not be specifically limited if it is a solvent in which compound (L) dissolves.
- alcohols such as methanol, ethanol, isopropanol, and normal propanol are preferably used as the organic solvent, and alcohols having the same molecular structure (alkoxy component) as the alkoxy group contained in the compound (L) are more preferably used. It is done.
- methanol is preferred for tetramethoxysilane and ethanol is preferred for tetraethoxysilane.
- the amount of the organic solvent to be used is not particularly limited, but is preferably an amount such that the concentration of the compound (L) is 1 to 90% by weight, more preferably 10 to 80% by weight, still more preferably 10 to 60% by weight. .
- the temperature of the reaction system is not necessarily limited when the compound (L) is hydrolyzed or condensed in the reaction system. However, it is usually in the range of 2 to 100 ° C, preferably in the range of 4 to 60 ° C, and more preferably in the range of 6 to 50 ° C.
- the reaction time varies depending on the reaction conditions such as the amount and type of the acid catalyst, but is usually in the range of 0.01 to 60 hours, preferably in the range of 0.1 to 12 hours, more preferably 0.8. The range is 1 to 6 hours.
- the reaction can be performed in an atmosphere of various gases such as air, carbon dioxide, nitrogen, and argon.
- the solution (U) can be prepared using the solution (T), the carboxylic acid-containing polymer, and, if necessary, water and an organic solvent.
- a method of adding and mixing the solution (T) to a solution in which the carboxylic acid-containing polymer is dissolved can be employed.
- the method of adding and mixing the solution which dissolved the carboxylic acid containing polymer in water or the organic solvent to the solution (T) is also employable.
- the solution (T) to be added or the solution in which the carboxylic acid-containing polymer is dissolved may be added at once or may be added in divided portions.
- the solution in which the carboxylic acid-containing polymer in step (id) is dissolved can be prepared by the following method. What is necessary is just to select the solvent to be used according to the kind of carboxylic acid containing polymer.
- a water-soluble polymer such as polyacrylic acid or polymethacrylic acid
- water is suitable.
- an alkaline substance such as ammonia, sodium hydroxide or potassium hydroxide is preferred.
- alcohols such as methanol and ethanol; ethers such as tetrahydrofuran, dioxane and trioxane; ketones such as acetone and methyl ethyl ketone; glycols such as ethylene glycol and propylene glycol, as long as the dissolution of the carboxylic acid-containing polymer is not hindered Glycol derivatives such as methyl cellosolve, ethyl cellosolve, n-butyl cellosolve; glycerin; acetonitrile, dimethylformamide, dimethyl sulfoxide, sulfolane, dimethoxyethane and the like can be used in combination.
- a part (for example, 0.1 to 10 mol%) of the —COO— group contained in the functional group (F) is neutralized by monovalent ions. May be.
- the degree of neutralization of the functional group (F) with monovalent ions is more preferably in the range of 0.5 to 5 mol% from the viewpoint of improving the transparency of the resulting gas barrier laminate. More preferably, it is in the range of ⁇ 3 mol%.
- monovalent ions include ammonium ions, pyridinium ions, sodium ions, potassium ions, and lithium ions, with ammonium ions being preferred.
- the solid content concentration of the solution (U) is preferably in the range of 3% by weight to 20% by weight from the viewpoint of the storage stability of the solution (U) and the coating property of the solution (U) on the substrate. It is more preferably in the range of 4% to 15% by weight, and still more preferably in the range of 5% to 12% by weight.
- the pH of the solution (U) is preferably in the range of 1.0 to 7.0, preferably 1.0 to 6 More preferably, it is in the range of 0.0, and more preferably in the range of 1.5 to 4.0.
- the pH of the solution (U) can be adjusted by a known method, for example, acidic compounds such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, butyric acid, ammonium sulfate, sodium hydroxide, potassium hydroxide, ammonia, trimethylamine, pyridine, It can adjust by adding basic compounds, such as sodium carbonate and sodium acetate. At this time, if a basic compound that provides a monovalent cation is used in the solution, a part of the carboxyl group and / or carboxylic anhydride group of the carboxylic acid-containing polymer may be neutralized with a monovalent ion. The effect that it can be obtained.
- acidic compounds such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, butyric acid, ammonium sulfate, sodium hydroxide, potassium hydroxide, ammonia, trimethylamine, pyridine.
- Step (ie) will be described.
- the state of the solution (U) prepared in the step (id) changes with time, and finally becomes a gel composition.
- the time until the solution (U) becomes gelled depends on the composition of the solution (U).
- the solution (U) In order to stably apply the solution (U) to the substrate, it is preferable that the solution (U) has a stable viscosity over a long period of time and then gradually increases in viscosity.
- the solution (U) was measured with a Brookfield viscometer (B-type viscometer: 60 rpm) even after standing at 25 ° C. for 2 days, based on the total amount of the compound (L) component.
- Is preferably adjusted to be 1 N ⁇ s / m 2 or less (more preferably 0.5 N ⁇ s / m 2 or less, particularly preferably 0.2 N ⁇ s / m 2 or less).
- the solution (U) has a viscosity of 1 N ⁇ s / m 2 or less (more preferably 0.1 N ⁇ s / m 2 or less, particularly preferably 0. It is more preferable to adjust the composition so as to be 05 N ⁇ s / m 2 or less.
- the solution (U) has a viscosity of 1 N ⁇ s / m 2 or less (more preferably 0.1 N ⁇ s / m 2 or less, particularly preferably 0. More preferably, the composition is adjusted to be 05 N ⁇ s / m 2 or less.
- adjusting the concentration of solids for example, adjusting pH, carboxymethylcellulose, starch, bentonite, tragacanth gum, stearate, alginate,
- a method of adding a viscosity modifier such as methanol, ethanol, n-propanol, or isopropanol can be used.
- an organic solvent that can be uniformly mixed with the solution (U) is added so long as the stability of the solution (U) is not hindered. May be.
- organic solvents that can be added include alcohols such as methanol, ethanol, n-propanol, and isopropanol; ethers such as tetrahydrofuran, dioxane, and trioxane; ketones such as acetone, methyl ethyl ketone, methyl vinyl ketone, and methyl isopropyl ketone; ethylene glycol, Glycols such as propylene glycol; glycol derivatives such as methyl cellosolve, ethyl cellosolve, n-butyl cellosolve; glycerin; acetonitrile, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane, dimethoxyethane
- solution (U) may be carbonate, hydrochloride, nitrate, hydrogen carbonate, sulfate, hydrogen sulfate, phosphate, borate, alumina as long as it does not impair the effects of the present invention.
- Inorganic acid metal salts such as acid salts; organic acid metal salts such as oxalate, acetate, tartrate and stearate; acetylacetonate metal complexes such as aluminum acetylacetonate; cyclopentadiene such as titanocene Metal complexes such as enyl metal complexes and cyano metal complexes; layered clay compounds, crosslinking agents, compounds containing two or more amino groups as described above (P), compounds containing two or more hydroxyl groups as described above (Q), and other It may contain a polymer compound, a plasticizer, an antioxidant, an ultraviolet absorber, a flame retardant and the like.
- the solution (U) may contain fine metal oxide powder or fine silica powder.
- the solution (U) prepared in the step (id) is applied to at least one surface of the substrate in the step (ie).
- the surface of the substrate may be treated with a known anchor coating agent, or a known adhesive may be applied to the surface of the substrate.
- the method for applying the solution (U) to the substrate is not particularly limited, and a known method can be used. Preferred methods include, for example, a casting method, a dipping method, a roll coating method, a gravure coating method, a screen printing method, a reverse coating method, a spray coating method, a kiss coating method, a die coating method, a metering bar coating method, and a chamber doctor combined coating method. And curtain coating method.
- the solvent contained in the solution (U) is removed to obtain a laminate (laminate (I)) before the ionization step. It is done.
- the method for removing the solvent is not particularly limited, and a known method can be applied. Specifically, methods such as a hot air drying method, a hot roll contact method, an infrared heating method, and a microwave heating method can be applied alone or in combination.
- the drying temperature is not particularly limited as long as it is 15 to 20 ° C. or more lower than the flow start temperature of the base material and 15 to 20 ° C. or more lower than the thermal decomposition start temperature of the carboxylic acid-containing polymer.
- the drying temperature is preferably in the range of 70 ° C to 200 ° C, more preferably in the range of 80 to 180 ° C, and further preferably in the range of 90 to 160 ° C.
- the removal of the solvent may be carried out under normal pressure or reduced pressure.
- a skin layer made of a hydrolyzable condensate of compound (L) is preferably formed on the surface of the gas barrier layer. Further, as described above, it is not preferable that the skin layer becomes too thick because the transparency of the gas barrier laminate is lowered.
- a method for forming a skin layer having an appropriate thickness will be described below. According to the results of intensive studies by the present inventors, the presence or absence of the skin layer and the state of the skin layer formation are determined by the reactivity of the hydrolyzable condensate of the compound (L), the composition of the compound (L), It depends on the solvent used in the solution (U), the drying speed of the solution (U) after the solution (U) is applied to the substrate, and the like.
- the reaction time in the step (ia) and the step (ic) is increased. It is possible to increase the contact angle (that is, to form an appropriate skin layer). On the contrary, when the contact angle is larger than the predetermined range, it is possible to reduce the contact angle by shortening the reaction time in the steps (ia) and (ic).
- the step (ii) By bringing the laminate (I) obtained by the above step into contact with a solution containing metal ions having a valence of 2 or more (hereinafter sometimes referred to as “solution (IW)”) by the step (ii) (ionization step).
- solution (IW) a solution containing metal ions having a valence of 2 or more
- the gas barrier laminate (laminate (II)) of the present invention is obtained.
- the ionization process may be performed at any stage as long as the effects of the present invention are not impaired.
- the ionization step may be performed before or after being processed into the form of the packaging material, or may be performed after the packaging material is filled with the contents and sealed.
- the solution (IW) can be prepared by dissolving in a solvent a compound (polyvalent metal compound) that releases metal ions having two or more valences upon dissolution.
- a solvent used in preparing the solution (IW) it is desirable to use water, but it may be a mixture of an organic solvent miscible with water and water.
- organic solvents examples include alcohols such as methanol, ethanol, n-propanol, and isopropanol; ethers such as tetrahydrofuran, dioxane, and trioxane; ketones such as acetone, methyl ethyl ketone, methyl vinyl ketone, and methyl isopropyl ketone; ethylene glycol, propylene glycol Glycols such as methyl cellosolve, ethyl cellosolve, and n-butyl cellosolve; glycerin; organic solvents such as acetonitrile, dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane, and dimethoxyethane.
- alcohols such as methanol, ethanol, n-propanol, and isopropanol
- ethers such as tetrahydrofuran, dioxane, and trioxane
- ketones such as
- compounds capable of releasing the metal ions exemplified for the gas barrier laminate of the present invention can be used.
- polyvalent metal compound Only one type of polyvalent metal compound may be used, or two or more types may be used in combination.
- Preferred polyvalent metal compounds include calcium acetate, calcium hydroxide, magnesium acetate, and zinc acetate. In addition, you may use these polyvalent metal compounds in the form of a hydrate.
- the concentration of the polyvalent metal compound in the solution (IW) is not particularly limited, but is preferably in the range of 5 ⁇ 10 ⁇ 4 wt% to 50 wt%, more preferably 1 ⁇ 10 ⁇ 2 wt% to 30 wt%. More preferably, it is in the range of 1% by weight to 20% by weight.
- the temperature of the solution (IW) is not particularly limited, but the higher the temperature, the faster the ionization rate of the carboxyl group-containing polymer.
- the temperature is, for example, in the range of 30 to 140 ° C., preferably in the range of 40 ° C. to 120 ° C., and more preferably in the range of 50 ° C. to 100 ° C.
- the method for removing the solvent is not particularly limited, and a known method can be applied. Specifically, drying methods such as a hot air drying method, a hot roll contact method, an infrared heating method, and a microwave heating method can be applied singly or in combination of two or more.
- the temperature at which the solvent is removed is not particularly limited as long as it is 15 to 20 ° C. or more lower than the flow start temperature of the substrate and 15 to 20 ° C. or lower than the thermal decomposition start temperature of the carboxylic acid-containing polymer.
- the drying temperature is preferably in the range of 40 to 200 ° C, more preferably in the range of 60 to 150 ° C, and still more preferably in the range of 80 to 130 ° C.
- the removal of the solvent may be carried out under normal pressure or reduced pressure.
- the solvent in which the polyvalent metal compound dissolves a solvent that can be used for the solution (IW) can be used, and the same solvent as the solvent for the solution (IW) is preferably used.
- the production method of the present invention further includes a step of heat-treating the layer formed in step (i) at a temperature of 120 to 240 ° C. after step (i) and before and / or after step (ii). But you can. That is, you may heat-process with respect to laminated body (I) or (II).
- the heat treatment may be performed at any stage as long as the removal of the solvent of the coated solution (U) is almost completed, but the layered product (that is, the layered product (I)) before the ionization step is performed. By performing the heat treatment, a gas barrier laminate having a good surface appearance can be obtained.
- the temperature of the heat treatment is preferably in the range of 120 ° C to 240 ° C, more preferably in the range of 140 to 240 ° C, and still more preferably in the range of 160 ° C to 220 ° C.
- the heat treatment can be performed in air, under a nitrogen atmosphere, under an argon atmosphere, or the like.
- the laminate (I) or (II) may be irradiated with ultraviolet rays.
- the ultraviolet irradiation may be performed any time after the removal of the solvent of the coated solution (U) is almost completed.
- the method is not particularly limited, and a known method can be applied.
- the wavelength of the ultraviolet rays to be irradiated is preferably in the range of 170 to 250 nm, more preferably in the range of 170 to 190 nm and / or in the range of 230 to 250 nm.
- radiation such as an electron beam or ⁇ -ray may be irradiated.
- Only one of heat treatment and ultraviolet irradiation may be performed, or both may be used in combination.
- the gas barrier performance of the laminate may be expressed to a higher degree.
- a treatment treatment with an anchor coating agent or application of an adhesive
- the substrate coated with the solution (U) is compared. It is preferable to perform an aging treatment that is allowed to stand at a low temperature for a long time.
- the temperature of the aging treatment is preferably in the range of 30 to 200 ° C, more preferably in the range of 30 to 150 ° C, and further preferably in the range of 30 to 120 ° C.
- the aging time is preferably in the range of 0.5 to 10 days, more preferably in the range of 1 to 7 days, and further preferably in the range of 1 to 5 days.
- the adhesive force between the base material and the gas barrier layer becomes stronger. It is preferable to perform the above heat treatment (heat treatment at 120 ° C. to 240 ° C.) after this aging treatment.
- the gas barrier laminate of the present invention has an excellent barrier property against gases such as oxygen, water vapor, carbon dioxide gas, nitrogen, etc., and the excellent barrier property is exposed to bending conditions even under high humidity conditions. Can hold highly. In addition, it exhibits excellent gas barrier properties even after retorting. Thus, the gas barrier laminate of the present invention has good gas barrier properties that are not affected by environmental conditions such as humidity, and exhibits high gas barrier properties even after being exposed to bending conditions, and thus can be applied to various applications. .
- the gas barrier laminate of the present invention is particularly useful as a food packaging material (particularly a retort food packaging material).
- the gas barrier laminate of the present invention can also be used as a packaging material for packaging chemicals such as agricultural chemicals and pharmaceuticals, industrial materials such as precision materials, and clothing.
- Measurement and evaluation in the following examples were performed by the following methods (1) to (9).
- description of the abbreviation used by the following description about a measuring method and an evaluation method may be mentioned later.
- description of the abbreviation used by the following description about a measuring method and an evaluation method may be mentioned later.
- description of a measurement result and an evaluation result it describes in the table
- Oxygen barrier property before retort treatment Oxygen permeability was measured using an oxygen permeation measuring device ("MOCON OX-TRAN 2/20" manufactured by Modern Control).
- the laminate was conditioned for 24 hours under conditions of a temperature of 23 ° C and a humidity of 50% RH. Thereafter, the laminate was cut into 15 cm ⁇ 15 mm with respect to the MD direction and the TD direction. The cut laminate was measured for tensile strength and Young's modulus by a method according to JIS-K7127 under the conditions of a temperature of 23 ° C. and a humidity of 50% RH.
- Dry heat shrinkage (%) (l b ⁇ l a ) ⁇ 100 / l b [Wherein lb represents a length before heating. l a represents the length after heating. ]
- the substrate was coated on the surface with a two-component anchor coating agent (Mitsui Takeda Chemical Co., Ltd., Takelac 626 (trade name) and Takenate A50 (trade name), hereinafter abbreviated as “AC”).
- a stretched nylon film manufactured by Unitika Ltd., Emblem ON-BC (trade name), thickness of 15 ⁇ m, hereinafter sometimes abbreviated as “ON”) was used.
- a standard sample [laminated body (layer made of neutralized polyacrylic acid / AC / ON)] having a carboxyl group neutralization degree of 0, 25, 50, 75, 80, and 90 mol% was prepared. Produced.
- the infrared absorption spectrum was measured in the mode of ATR (total reflection measurement) using the Fourier-transform infrared spectrophotometer (The product made from Perkin Elmer, Spectrum One).
- the two peaks corresponding to the C O stretching vibration in the layer consisting of neutralized product of polyacrylic acid, i.e., a peak observed in the range of 1600 cm -1 ⁇ 1850 cm -1 and 1500 cm -1 ⁇ 1600 cm -
- the ratio of the maximum absorbance was calculated for the peak observed in the range of 1 .
- the calibration curve 1 was created using the calculated ratio and the ionization degree of each standard sample.
- the degree of ionization was calculated using the calibration curve 2 obtained by fluorescent X-ray intensity measurement.
- the pouch was placed in a retort treatment apparatus (manufactured by Nisaka Seisakusho, Flavor Ace RCS-60) and subjected to retort treatment at 120 ° C. for 30 minutes and 0.15 MPa. After the retort treatment, heating was stopped, and the pouch was taken out from the retort treatment device when the internal temperature of the retort treatment device reached 60 ° C. Then, the pouch was left for 1 hour in a room at 20 ° C. and 65% RH. Thereafter, the heat-sealed portion was cut off with scissors, and the water adhering to the surface of the laminate was wiped off by lightly pressing a paper towel.
- a retort treatment apparatus manufactured by Nisaka Seisakusho, Flavor Ace RCS-60
- the pouch was left in a desiccator adjusted to 20 ° C. and 85% RH for one day or longer.
- the oxygen barrier property after the retort treatment was evaluated by measuring the oxygen permeability of the laminate subjected to such a retort treatment.
- the oxygen transmission rate was measured using an oxygen transmission amount measuring device (“MOCON OX-TRAN 2/20” manufactured by Modern Control). Specifically, the laminate is set so that the gas barrier layer faces the oxygen supply side and the CPP faces the carrier gas side, the temperature is 20 ° C., the humidity is 85% RH on the oxygen supply side, the humidity is 85% RH on the carrier gas side, The oxygen permeability (unit: cc / m 2 / day / atm) was measured under conditions of an oxygen pressure of 1 atm and a carrier gas pressure of 1 atm.
- the laminated body of each Example has an oxygen barrier property before and after the retort treatment in comparison with the laminated bodies of Reference Examples 1 and 2 even though the coat layer is thin. It was equivalent or better and was excellent in gas barrier properties and hot water resistance. Furthermore, the laminated body of each Example was approaching the performance of the base film itself shown in Reference Examples 3 and 4 with respect to tensile strength and elongation and Young's modulus. Moreover, the laminated body of each Example was improved compared with the laminated body of the reference examples 1 and 2 regarding the dry heat shrinkage rate. That is, the laminated body of each Example was excellent in workability. In addition, when the retort treatment was performed under severe conditions, the laminates of Reference Examples 1 and 2 slightly changed the appearance, but the laminates of the examples did not change the appearance, and the laminates of the examples were excellent. Showed hot water resistance.
- the reaction time at the time of preparing the mixed liquid (T) was 1 hour, and in the subsequent examples, the reaction time was 5 hours.
- the contact angle of the gas barrier layer could be increased and the skin layer could be made thicker.
- the wet gas barrier layers are stacked on top of each other. Even when placed, the gas barrier layers did not stick together.
- PAA Polyacrylic acid
- 150,000 was dissolved in distilled water to obtain a PAA aqueous solution having a solid content concentration of 13% by weight in the aqueous solution.
- 13% ammonia aqueous solution was added to this PAA aqueous solution to neutralize 1 mol% of the carboxyl group of PAA, thereby obtaining a partially neutralized aqueous solution of PAA.
- AIP aluminum isopropoxide
- TMOS tetramethoxysilane
- AIP aqueous solution
- a two-component anchor coating agent dissolved in 67 parts by weight of ethyl acetate (Mitsui Takeda Chemical Co., Ltd .: Takelac A-626 (trade name) 1 part by weight and Takenate A-50 (trade name) 2 parts by weight) Is coated on a stretched polyethylene terephthalate film (manufactured by Toray Industries, Inc., Lumirror P60 (trade name), thickness 12 ⁇ m, hereinafter sometimes abbreviated as “PET”) and dried to form a base having an anchor coat layer A material (AC (0.1 ⁇ m) / PET (12 ⁇ m)) was prepared.
- an anchor coat layer A material AC (0.1 ⁇ m) / PET (12 ⁇ m)
- the mixed solution (U1) was coated on the anchor coat layer of the base material with a bar coater so that the thickness after drying was 0.4 ⁇ m, and dried at 120 ° C. for 5 minutes. Subsequently, coating was also performed on the opposite surface of the substrate in the same procedure.
- the obtained laminate was aged at 40 ° C. for 3 days. Next, the laminate was heat-treated at 180 ° C. for 5 minutes using a dryer. Next, the laminate was immersed in a 2% by weight calcium acetate aqueous solution (85 ° C.) for 12 seconds, and then dried at 110 ° C. for 1 minute.
- a laminate (A1) having a structure of gas barrier layer (0.4 ⁇ m) / AC (0.1 ⁇ m) / PET (12 ⁇ m) / AC (0.1 ⁇ m) / gas barrier layer (0.4 ⁇ m) is obtained. It was. With respect to the laminate (A1), the ionization degree, the oxygen permeability before retorting, the contact angle, the tensile strength and elongation, the Young's modulus, and the dry heat shrinkage ratio were measured by the methods described above.
- Example 2 A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in Example 1.
- the molar ratio of Al / Si is 30.1 / 69.9, and the weight ratio of [inorganic component derived from TMOS and AIP] / [partially neutralized product of PAA] is 25.5 / 74.5.
- a mixed solution (U2) was prepared. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 293 parts by weight of a 9.88% by weight AIP aqueous solution (S2) was added thereto.
- Example 2 Using the mixed solution (U2), coating, heat treatment, ionization and drying were performed in the same manner as in Example 1 to obtain a laminate (A2). Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (2). Evaluation of the laminate and laminate was performed in the same manner as in Example 1.
- Examples 3 to 5 an Al compound, a Ti compound, and a Zr compound were used as the compound (A). Although any compound was used, high gas barrier properties and hot water resistance were exhibited, but the Al compound was excellent from the viewpoint of better gas barrier properties before and after retorting.
- Example 3 A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in Example 1. And only the reaction time was changed and the liquid mixture (U3) was prepared.
- TMOS TMOS aqueous solution
- S3 a 9.88% by weight AIP aqueous solution
- 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalents, and hydrolysis and condensation reactions were carried out at 10 ° C. for 5 hours. And a liquid mixture (T3) was obtained.
- TIP titanium tetraisopropoxide
- TMOS TMOS aqueous solution
- S4 TIP aqueous solution
- 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalent, and hydrolysis and condensation reaction was performed at 10 ° C. for 5 hours.
- T4 a liquid mixture
- U4 a mixed liquid having a solid content concentration of 5% by weight was obtained by the same composition and method as in Example 1.
- Example 1 Using the mixed solution (U4), coating, heat treatment, ionization, and drying were performed in the same manner as in Example 1 to obtain a laminate (A4). Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (4). Evaluation of the laminate and laminate was performed in the same manner as in Example 1.
- ZIP zirconium tetraisopropoxide
- TMOS TMOS
- S5 9.8% by weight ZIP aqueous solution
- 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalent, and hydrolysis and condensation reaction was performed at 10 ° C. for 5 hours.
- a liquid mixture (T5) was obtained.
- a mixed solution (U5) having a solid concentration of 5% by weight was obtained by the same composition and method as in Example 1.
- Example 5 Using the mixed solution (U5), coating, heat treatment, ionization and drying were performed in the same manner as in Example 1 to obtain a laminate (A5). Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (5). Evaluation of the laminate and laminate was performed in the same manner as in Example 1.
- the ratio of [number of moles of M 1 atom derived from compound (A)] / [number of moles of Si atom derived from compound (B)] is 1.2 / 98. It is preferably in the range of 8 to 30.0 / 70.0 (see Example 6), more preferably in the range of 1.9 / 98.1 to 30.0 / 70.0 (Example 7) and more preferably in the range of 2.8 / 97.2 to 30.0 / 70.0 (see Example 8).
- Example 6 A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in Example 1.
- the mixed solution was prepared in the same ratio as in Example 3 except that the weight ratio of [inorganic component derived from TMOS and AIP] / [partially neutralized product of PAA] was 30.2 / 69.8. (U6) was prepared.
- a mixed solution (T6) was prepared by the same composition and method as the mixed solution (T3) obtained in Example 3.
- Example 6 Using the mixed solution (U6), coating, heat treatment, ionization and drying were performed in the same manner as in Example 1 to obtain a laminate (A6). Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (6). Evaluation of the laminate and the laminate was performed in the same manner as in Example 1.
- Example 7 A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in Example 1. And the liquid mixture (U7) was prepared by the preparation ratio similar to Example 6 except having made it the molar ratio of Al / Si becoming 1.9 / 98.1. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 13.2 parts by weight of the 9.88 wt% AIP aqueous solution (S7) was added thereto. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalent, and hydrolysis and condensation reaction was performed at 10 ° C. for 5 hours. And a liquid mixture (T7) was obtained. Then, the liquid mixture (U7) whose solid content concentration is 5 weight% with the composition and method similar to Example 6 was obtained.
- Example 7 Using the mixed solution (U7), coating, heat treatment, ionization and drying were performed in the same manner as in Example 1 to obtain a laminate (A7). Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (7). Evaluation of the laminate and laminate was performed in the same manner as in Example 1. Furthermore, the oxygen permeability after 10% elongation was also measured.
- Example 8> A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in Example 1. And the liquid mixture (U8) was prepared by the preparation ratio similar to Example 6 except having made it the molar ratio of Al / Si becoming 2.8 / 97.2. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 19.8 parts by weight of the 9.88 wt% AIP aqueous solution (S8) was added thereto. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalent, and hydrolysis and condensation reaction was performed at 10 ° C. for 5 hours. And a liquid mixture (T8) was obtained. Then, the liquid mixture (U8) whose solid content concentration is 5 weight% by the same composition and method as Example 6 was obtained.
- Example 1 Using the mixed solution (U8), coating, heat treatment, ionization and drying were performed in the same manner as in Example 1 to obtain a laminate (A8). Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (8). Evaluation of the laminate and laminate was performed in the same manner as in Example 1.
- Example 9 A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in Example 1.
- a mixed solution (U9) was prepared so as to be 0.5. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 293 parts by weight of a 9.88 wt% AIP aqueous solution (S9) was added thereto.
- Example 1 Using the mixed solution (U9), coating, heat treatment, ionization and drying were performed in the same manner as in Example 1 to obtain a laminate (A9). Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (9). Evaluation of the laminate and laminate was performed in the same manner as in Example 1.
- Example 10 A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in Example 1.
- the molar ratio of Al / Si is 0.1 / 99.9, and the weight ratio of [inorganic component derived from TMOS and AIP] / [partially neutralized product of PAA] is 80.0 / 20.0.
- a mixed solution (U10) was prepared. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 0.7 part by weight of a 9.88 wt% AIP aqueous solution (S10) was added thereto.
- Example 10 Using the mixed solution (U10), coating, heat treatment, ionization and drying were performed in the same manner as in Example 1 to obtain a laminate (A10). Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (10). Evaluation of the laminate and laminate was performed in the same manner as in Example 1.
- Example 11 A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in Example 1.
- the molar ratio of Al / Si is 29.9 / 70.1
- the weight ratio of [inorganic component derived from TMOS and AIP] / [partially neutralized product of PAA] is 36.9 / 63.1.
- a mixed solution (U11) was prepared. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 290 parts by weight of a 9.88 wt% AIP aqueous solution (S11) was added thereto.
- Example 1 Using the mixed solution (U11), coating, heat treatment, ionization and drying were performed in the same manner as in Example 1 to obtain a laminate (A11). Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (11). Evaluation of the laminate and laminate was performed in the same manner as in Example 1.
- Example 12 A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in Example 1.
- the molar ratio of Al / Si is 0.1 / 99.9, and the weight ratio of [inorganic component derived from TMOS and AIP] / [partially neutralized product of PAA] is 70.0 / 30.0.
- a mixed solution (U12) was prepared. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 0.7 part by weight of a 9.88 wt% AIP aqueous solution (S12) was added thereto.
- Example 1 Using the mixed solution (U12), coating, heat treatment, ionization and drying were performed in the same manner as in Example 1 to obtain a laminate (A12). Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (12). Evaluation of the laminate and laminate was performed in the same manner as in Example 1.
- the ratio of the total to the weight of the organic component derived from is preferably in the range of 20.0 / 80.0 to 80.0 / 20.0 (see Examples 13, 14, 16, and 17), More preferably, it is in the range of 30.5 / 69.5 to 70.0 / 30.0 (see Examples 8 and 15).
- Example 13 A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in Example 1.
- the molar ratio of Al / Si is 3.0 / 97.0, and the weight ratio of [inorganic component derived from TMOS and AIP] / [partially neutralized product of PAA] is 20.0 / 80.0.
- a mixed solution (U13) was prepared. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 20.8 parts by weight of a 9.88 wt% AIP aqueous solution (S13) was added thereto.
- Example 1 Using the mixed solution (U13), coating, heat treatment, ionization and drying were performed in the same manner as in Example 1 to obtain a laminate (A13). Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (13). Evaluation of the laminate and laminate was performed in the same manner as in Example 1.
- Example 14 A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in Example 1.
- the molar ratio of Al / Si is 3.0 / 97.0 and the weight ratio of [inorganic component derived from TMOS and AIP] / [partially neutralized product of PAA] is 80.0 / 20.0.
- a mixed solution (U14) was prepared. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 21.0 parts by weight of a 9.88 wt% AIP aqueous solution (S14) was added thereto.
- Example 1 Using the mixed solution (U14), coating, heat treatment, ionization and drying were performed in the same manner as in Example 1 to obtain a laminate (A14). Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (14). Evaluation of the laminate and laminate was performed in the same manner as in Example 1.
- Example 15 A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in Example 1.
- the molar ratio of Al / Si is 3.0 / 97.0, and the weight ratio of [inorganic component derived from TMOS and AIP] / [partially neutralized product of PAA] is 70.0 / 30.0.
- a mixed solution (U15) was prepared. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 21.1 parts by weight of a 9.88 wt% AIP aqueous solution (S15) was added thereto.
- Example 1 Using the mixed solution (U15), coating, heat treatment, ionization and drying were performed in the same manner as in Example 1 to obtain a laminate (A15). Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (15). Evaluation of the laminate and laminate was performed in the same manner as in Example 1.
- Example 16 A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in Example 1.
- the molar ratio of Al / Si is 2.9 / 97.1
- the weight ratio of [inorganic component derived from TMOS and AIP] / [partially neutralized product of PAA] is 10.2 / 89.8.
- a mixed solution (U16) was prepared. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 20.3 parts by weight of a 9.88 wt% AIP aqueous solution (S16) was added thereto.
- Example 1 Using the mixed solution (U16), coating, heat treatment, ionization and drying were performed in the same manner as in Example 1 to obtain a laminate (A16). Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (16). Evaluation of the laminate and laminate was performed in the same manner as in Example 1.
- Example 17 A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in Example 1.
- the molar ratio of Al / Si is 3.0 / 97.0, and the weight ratio of [inorganic component derived from TMOS and AIP] / [partially neutralized product of PAA] is 90.2 / 9.8.
- a mixed solution (U17) was prepared. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 21.3 parts by weight of a 9.88 wt% AIP aqueous solution (S17) was added thereto.
- Example 1 Using the mixed solution (U17), coating, heat treatment, ionization and drying were performed in the same manner as in Example 1 to obtain a laminate (A17). Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (17). Evaluation of the laminate and laminate was performed in the same manner as in Example 1.
- Example 18 A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in Example 1. Subsequently, the molar ratio of TMOS / ⁇ -glycidoxydoxypropyltrimethoxysilane (GPTMOS) was 99.5 / 0.5, the molar ratio of Al / Si was 2.8 / 97.2, [TMOS, AIP and A mixed solution (U18) was prepared so that the weight ratio of [inorganic component derived from GPTMOS] / [partially neutralized product of organic component of GPTMOS and PAA] was 30.5 / 69.5.
- GPTMOS ⁇ -glycidoxydoxypropyltrimethoxysilane
- TMOS and GPTMOS were dissolved in 50 parts by weight of methanol, and a 9.88 wt% AIP aqueous solution (S18) prepared in the same manner as in Example 1 was added thereto. 19.6 parts by weight were added. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to the total of TMOS and GPTMOS was 1.95 molar equivalent, and the mixture was hydrolyzed at 10 ° C. for 5 hours. Decomposition
- disassembly and condensation reaction were performed and the liquid mixture (T18) was obtained.
- Example 1 Using the mixed solution (U18), coating, heat treatment, ionization and drying were performed in the same manner as in Example 1 to obtain a laminate (A18). Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (18). Evaluation of the laminate and laminate was performed in the same manner as in Example 1.
- Example 19 A mixed liquid (U19) was obtained with the same charging ratio as in Example 18 except that the molar ratio of TMOS / GPTMOS was 80.0 / 20.0. Specifically, first, 36.0 parts by weight of TMOS and 14.0 parts by weight of GPTMOS were dissolved in 50 parts by weight of methanol, and 19.8 parts by weight of a 9.88% by weight AIP aqueous solution (S19) was added thereto. Further, 3.0 parts by weight of distilled water and 7.4 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to the total of TMOS and GPTMOS was 1.95 molar equivalents, and water was added at 10 ° C. for 5 hours.
- T19 Decomposition and condensation reaction were performed to obtain a mixed solution (T19). Subsequently, after the mixed liquid (T19) was diluted with 520 parts by weight of distilled water and 302 parts by weight of methanol, 267 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight) was rapidly added while stirring. A liquid mixture (U19) having a solid content concentration of 5% by weight was obtained.
- Example 7 Using the mixed solution (U19), coating, heat treatment, ionization and drying were performed in the same manner as in Example 1 to obtain a laminate (A19). Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (19). Evaluation of the laminate and the laminate was performed in the same manner as in Example 7.
- Example 20 A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in Example 1. Subsequently, the molar ratio of TMOS / GPTMOS is 89.9 / 10.1, the molar ratio of Al / Si is 3.1 / 96.9, [inorganic components derived from TMOS, AIP and GPTMOS] / [organic of GPTMOS] The mixed solution (U20) was prepared so that the weight ratio of the component and the partially neutralized product of PAA was 31.5 / 68.5.
- TMOS and 7.4 parts by weight of GPTMOS were dissolved in 50 parts by weight of methanol, and 20.6 parts by weight of a 9.88% by weight AIP aqueous solution (S20) was added thereto. Further, 3.2 parts by weight of distilled water and 7.8 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to the total of TMOS and GPTMOS was 1.95 molar equivalents, and water was added at 10 ° C. for 5 hours. Decomposition
- disassembly and condensation reaction were performed and the liquid mixture (T20) was obtained.
- Example 7 Using the mixed solution (U20), coating, heat treatment, ionization and drying were performed in the same manner as in Example 1 to obtain a laminate (A20). Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (20). Evaluation of the laminate and the laminate was performed in the same manner as in Example 7.
- Example 21 A mixed liquid (U21) was obtained with the same charging ratio as in Example 18 except that the molar ratio of TMOS to GPTMOS was 98.0 / 2.0. Specifically, first, 48.5 parts by weight of TMOS and 1.5 parts by weight of GPTMOS were dissolved in 50 parts by weight of methanol, and 19.2 parts by weight of a 9.88% by weight AIP aqueous solution (S21) was added thereto. Further, 3.3 parts by weight of distilled water and 8.1 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to the total of TMOS and GPTMOS was 1.95 molar equivalent, and the mixture was hydrolyzed at 10 ° C. for 5 hours.
- T21 Decomposition and condensation reaction were performed to obtain a mixed solution (T21). Subsequently, after the mixture (T21) was diluted with 562 parts by weight of distilled water and 285 parts by weight of methanol, 345 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight) was rapidly added while stirring. This was added to obtain a mixed solution (U21) having a solid content concentration of 5% by weight.
- Example 7 Using the mixed solution (U21), coating, heat treatment, ionization and drying were performed in the same manner as in Example 1 to obtain a laminate (A21). Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (21). Evaluation of the laminate and the laminate was performed in the same manner as in Example 7.
- Example 22 A mixed liquid (U22) was obtained at the same charging ratio as in Example 18 except that the molar ratio of TMOS / GPTMOS was 99.9 / 0.1. Specifically, first, 49.9 parts by weight of TMOS and 0.1 part by weight of GPTMOS were dissolved in 50 parts by weight of methanol, and 21.0 parts by weight of a 9.88 wt% AIP aqueous solution (S22) was added thereto. Further, 3.3 parts by weight of distilled water and 8.1 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to the total of TMOS and GPTMOS was 1.95 molar equivalent, and the mixture was hydrolyzed at 10 ° C.
- Example 1 Using the mixed solution (U22), coating, heat treatment, ionization and drying were performed in the same manner as in Example 1 to obtain a laminate (A22). Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (22). Evaluation of the laminate and laminate was performed in the same manner as in Example 1.
- Example 23 A mixed liquid (U23) was obtained with the same charging ratio as in Example 18 except that the molar ratio of TMOS / GPTMOS was 70.0 / 30.0. Specifically, first, 30.0 parts by weight of TMOS and 20.0 parts by weight of GPTMOS were dissolved in 50 parts by weight of methanol, and 17.9 parts by weight of a 9.88% by weight AIP aqueous solution (S23) was added thereto. Further, 2.9 parts by weight of distilled water and 7.0 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to the total of TMOS and GPTMOS was 1.95 molar equivalent, and hydrolysis was carried out at 10 ° C. for 5 hours.
- a condensation reaction was performed to obtain a mixed solution (T23). Subsequently, after the mixed solution (T23) was diluted with 500 parts by weight of distilled water and 310 parts by weight of methanol, 229 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight) was rapidly added while stirring. A liquid mixture (U23) having a solid content concentration of 5% by weight was obtained.
- Example 7 Using the mixed solution (U23), coating, heat treatment, ionization and drying were performed in the same manner as in Example 1 to obtain a laminate (A23). Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (23). Evaluation of the laminate and the laminate was performed in the same manner as in Example 7.
- the degree of ionization is preferably 60 mol% or more and 100 mol% or less, and more preferably 80 mol% or more. Moreover, it was shown from the comparison with these Examples and the comparative example 8 that high ionized water resistance and gas barrier property will not be expressed if ionization is not performed.
- Example 24 the liquid mixture (U24) obtained by the composition and method similar to the liquid mixture (U21) obtained in Example 21 was used.
- a laminate was produced by performing coating and heat treatment in the same manner as in Example 1. This laminate was ionized by immersion in a 0.1 wt% calcium acetate aqueous solution (85 ° C.) for 12 seconds, and then dried in the same manner as in Example 1 to obtain a laminate (A24).
- Example 2 Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (24). Evaluation of the laminate and laminate was performed in the same manner as in Example 1.
- Example 25 the liquid mixture (U25) obtained by the same composition and method as the liquid mixture (U21) obtained in Example 21 was used.
- a laminate was produced by performing coating and heat treatment in the same manner as in Example 1. This laminate was ionized by being immersed in a 0.2 wt% aqueous calcium acetate solution (85 ° C.) for 6 seconds, and then dried in the same manner as in Example 1 to obtain a laminate (A25).
- Example 2 Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (25). Evaluation of the laminate and laminate was performed in the same manner as in Example 1.
- Example 26 the liquid mixture (U26) obtained by the same composition and method as the liquid mixture (U21) obtained in Example 21 was used.
- a laminate was produced by performing coating and heat treatment in the same manner as in Example 1. This laminate was ionized by immersion in a 0.2 wt% calcium acetate aqueous solution (85 ° C.) for 12 seconds, and then dried in the same manner as in Example 1 to obtain a laminate (A26).
- Example 2 Evaluation of the laminate and laminate was performed in the same manner as in Example 1.
- Example 27 the liquid mixture (U27) obtained by the same composition and method as the liquid mixture (U21) obtained in Example 21 was used.
- a laminate was produced by performing coating and heat treatment in the same manner as in Example 1. This laminate was ionized by immersing it in a 2 wt% aqueous magnesium acetate solution (85 ° C.) for 12 seconds, and then dried in the same manner as in Example 1 to obtain a laminate (A27).
- Example 2 Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (27). Evaluation of the laminate and laminate was performed in the same manner as in Example 1.
- Example 28 the liquid mixture (U28) obtained by the same composition and method as the liquid mixture (U21) obtained in Example 21 was used.
- a laminate was obtained by performing coating and heat treatment in the same manner as in Example 1. This laminate was ionized by immersing it in a 2 wt% aqueous zinc acetate solution (85 ° C.) for 12 seconds, and then dried in the same manner as in Example 1 to obtain a laminate (A28).
- Example 2 Evaluation of the laminate and laminate was performed in the same manner as in Example 1.
- Example 7 and Example 29 were compared to evaluate the effect of using a compound (P) containing two or more amino groups. From these examples, it was confirmed that the use of the compound (P) improves the hot water resistance of the laminate, that is, the oxygen barrier property after the retort treatment.
- Example 29 A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in Example 1.
- EDA was dissolved in 1N hydrochloric acid so that the molar ratio of ethylenediamine (EDA) / HCl was 1/2 to obtain an aqueous EDA hydrochloride solution.
- the mixed solution (U29) was prepared at the same charging ratio as in Example 7 except that the EDA hydrochloride aqueous solution was added so that the equivalent ratio of [amino group of EDA] / [carboxyl group of PAA] was 1.9 / 100. ) was prepared.
- the mixture (T29) prepared by the same composition and method as the mixture (T7) of Example 7 was diluted with 567 parts by weight of distilled water and 283 parts by weight of methanol, and then stirred. 354 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight) was quickly added, and further 12.7 parts by weight of an aqueous EDA hydrochloride solution was added to obtain a mixed liquid (U29) having a solid content concentration of 5% by weight. .
- Example 1 Using the mixed solution (U29), coating, heat treatment, ionization and drying were performed in the same manner as in Example 1 to obtain a laminate (A29). Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (29). Evaluation of the laminate and laminate was performed in the same manner as in Example 1.
- Example 7 and Example 30 were compared to evaluate the effect of using a compound (Q) containing two or more hydroxyl groups. From these examples, it is confirmed that the use of the compound (Q) improves the hot water resistance (that is, oxygen barrier property after retorting) and elongation resistance (that is, oxygen barrier property after elongation) of the laminate. It was.
- Example 30 A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in Example 1.
- polyvinyl alcohol manufactured by Kuraray Co., Ltd., PVA117, hereinafter sometimes abbreviated as “PVA”
- PVA polyvinyl alcohol
- the mixed solution (U27) was added at the same charging ratio as in Example 7 except that the PVA aqueous solution was added so that the equivalent ratio of [hydroxyl group of PVA] / [carboxyl group of PAA] was 18.2 / 100. Obtained. Specifically, first, the mixture (T30) prepared by the same composition and method as the mixture (T7) of Example 7 was diluted with 567 parts by weight of distilled water and 283 parts by weight of methanol, and then stirred.
- Example 7 Using the mixed solution (U30), coating, heat treatment, ionization and drying were performed in the same manner as in Example 1 to obtain a laminate (A30). Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (30). Evaluation of the laminate and the laminate was performed in the same manner as in Example 7.
- Example 21 the type of compound (D) in preparing the solution (S) was changed. From these examples, it was confirmed that by using acetic acid or propionic acid as the compound (D), the gas barrier properties before and after the retort treatment were improved.
- a mixed liquid (U31) was obtained by the same composition and method as the mixed liquid (U21) of Example 18 except that this AIP aqueous solution (S31) was used.
- Example 1 Using the mixed solution (U31), coating, heat treatment, ionization and drying were performed in the same manner as in Example 1 to obtain a laminate (A31). Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (31). Evaluation of the laminate and laminate was performed in the same manner as in Example 1.
- a mixed liquid (U32) was obtained by the same composition and method as the mixed liquid (U21) of Example 21 except that this AIP aqueous solution (S32) was used.
- Example 1 Using the mixed solution (U32), coating, heat treatment, ionization and drying were performed in the same manner as in Example 1 to obtain a laminate (A32). Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (32). Evaluation of the laminate and laminate was performed in the same manner as in Example 1.
- Example 21 the gas barrier layer was formed on both surfaces of the base material, but in Example 33, the gas barrier layer was formed only on one side of the base material. From these examples, when the gas barrier layer is present only on one side of the substrate, the gas barrier property of the laminate is slightly lowered, but the Young's modulus of the laminate approaches the Young's modulus of the substrate (Reference Example 3). It was confirmed that the workability of the body was improved.
- Example 33 the liquid mixture (U33) obtained by the same composition and method as the liquid mixture (U21) obtained in Example 21 was used. Except that the gas barrier layer was formed only on one side of the substrate, coating, heat treatment, ionization, and drying were performed in the same manner as in Example 1 to obtain a laminate (A33).
- a laminate (33) having a structure of PET / AC / gas barrier layer / adhesive / ON / adhesive / CPP was obtained in the same manner as in Example 1. Evaluation of the laminate and the laminate was performed in the same manner as in Example 7.
- Example 34 and 35 the type of substrate was changed from PET to ON. From these examples, it was confirmed that the gas barrier property was better when PET was used as the substrate than when ON was used. In addition, from the viewpoint of gas barrier properties, it was confirmed that PET is more suitable as a substrate. However, when the substrate of the laminate is turned ON, since the ON itself has strength, the configuration of the laminate is changed from a three-layer configuration such as a laminate / ON / CPP to a two-layer configuration such as a laminate / CPP. Since it can be simplified, there is an advantage that it is excellent in workability.
- Example 34 the liquid mixture (U34) obtained by the same composition and method as the liquid mixture (U8) obtained in Example 8 was used. In addition, coating, heat treatment, ionization, and drying were performed in the same manner as in Example 1 except that the base material was a stretched nylon film (“ON” described above) to obtain a laminate (B34).
- the base material was a stretched nylon film (“ON” described above) to obtain a laminate (B34).
- a two-component adhesive manufactured by Mitsui Takeda Chemical Co., Ltd., A-385 (trade name) and A-50 (trade name)
- CPP unstretched polypropylene film
- a dried product was prepared and laminated with the laminate (B34).
- a laminate (34) having a structure of gas barrier layer / AC / ON / AC / gas barrier layer / adhesive / CPP was obtained. Evaluation of the laminate and the laminate was performed in the same manner as in Example 7.
- Example 35 the liquid mixture (U35) obtained by the same composition and method as the liquid mixture (U21) obtained in Example 21 was used. Further, coating, heat treatment, ionization and drying were carried out in the same manner as in Example 34 to obtain a laminate (B35).
- Example 34 lamination was performed in the same manner as in Example 34 to obtain a laminate (35). Evaluation of the laminate and the laminate was performed in the same manner as in Example 7.
- Example 36 the liquid mixture (U36) obtained by the same composition and method as the liquid mixture (U8) obtained in Example 8 was used. Further, coating, heat treatment, ionization and drying were carried out in the same manner as in Example 34 to obtain a laminate (B36).
- a two-component adhesive (A-385 (product of Mitsui Takeda Chemical Co., Ltd.)) is used for each of a stretched polyethylene terephthalate film (“PET” described above) and an unstretched polypropylene film (“CPP” described above). Name) and A-50 (trade name)) were dried and prepared, and laminated with the laminate (B36). In this way, a laminate (36) having a structure of PET / adhesive / gas barrier layer / AC / ON / AC / gas barrier layer / adhesive / CPP was obtained. Evaluation of the laminate and laminate was performed in the same manner as in Example 1.
- Example 37 the liquid mixture (U37) obtained by the same composition and method as the liquid mixture (U21) obtained in Example 21 was used. Further, coating, heat treatment, ionization and drying were carried out in the same manner as in Example 34 to obtain a laminate (B37).
- Example 36 laminate (37). Evaluation of the laminate and laminate was performed in the same manner as in Example 1.
- Example 35 the gas barrier layer was formed on both surfaces of the substrate, but in Example 38, the gas barrier layer was formed only on one surface of the substrate. From these examples, when the gas barrier layer is present only on one side of the substrate, the gas barrier property of the laminate is slightly lowered, but the Young's modulus of the laminate approaches the Young's modulus of the substrate (Reference Example 4), and It was confirmed that the workability of the body was improved.
- Example 38 the liquid mixture (U38) obtained by the same composition and method as the liquid mixture (U21) obtained in Example 21 was used. Moreover, except having formed the gas barrier layer only in the single side
- Example 34 lamination was performed in the same manner as in Example 34 to obtain a laminate (38) having a structure of gas barrier layer / AC / ON / adhesive / CPP. Evaluation of the laminate and laminate was performed in the same manner as in Example 1.
- Reference Examples 1 and 2 are laminates in which PET and ON are used as the base material, the compound (A) is not used, and the thickness of the coating layer is 1 ⁇ m.
- the coat layer (gas barrier layer) in the laminate is thick, the gas barrier property is excellent, but the tensile strength and Young's modulus are greatly different from those of the base film, and the workability is lowered, for example, the dry heat shrinkage rate is large.
- the compound (A) was not used, the appearance of the pouch deteriorated when the retort treatment was performed under severe conditions.
- the molar ratio of TMOS / GPTMOS was 89.9 / 10.1, and the weight ratio of [inorganic component derived from TMOS and GPTMOS] / [partially neutralized product of organic component of GPTMOS and PAA] was 31.
- a mixed solution (T39) was prepared so as to be 5 / 68.5. Specifically, first, 46 parts by weight of TMOS and 8 parts by weight of GPTMOS were dissolved in 50 parts by weight of methanol.
- a partially neutralized aqueous solution of PAA was prepared in the same manner as in Example 1.
- a partially neutralized aqueous solution of PAA was prepared in the same manner as in Example 1.
- 308 parts by weight of a partially neutralized aqueous solution of PAA was rapidly added while stirring to obtain a solid content concentration of 13% by weight.
- a liquid mixture (U39) was obtained.
- a two-component anchor coating agent dissolved in 67 parts by weight of ethyl acetate (Mitsui Takeda Chemical Co., Ltd .: Takelac A-626 (trade name) 1 part by weight and Takenate A-50 (trade name) 2 parts by weight) was coated on a stretched polyethylene terephthalate film (“PET” described above) and dried to prepare a substrate (AC (0.1 ⁇ m) / PET (12 ⁇ m)) having an anchor coat layer.
- the mixed solution (U39) was coated with a bar coater so that the thickness after drying was 1.0 ⁇ m, and dried at 120 ° C. for 5 minutes.
- both sides of the substrate were coated to obtain a laminate.
- This laminate was aged at 40 ° C. for 3 days. Subsequently, the laminate was heat-treated at 180 ° C. for 5 minutes using a dryer. Next, the laminate was immersed in a 2% by weight calcium acetate aqueous solution (85 ° C.) for 12 seconds and then dried at 50 ° C. for 5 minutes. In this way, a laminate (A39) having a structure of gas barrier layer (1.0 ⁇ m) / AC (0.1 ⁇ m) / PET (12 ⁇ m) / AC (0.1 ⁇ m) / gas barrier layer (1.0 ⁇ m) is obtained. It was. The gas barrier layer was colorless and transparent and had a very good appearance.
- the oxygen transmission rate before contact with the retort treatment the contact angle, the tensile strength and elongation, the Young's modulus, and the dry heat shrinkage rate were measured by the aforementioned methods.
- Example 7 Evaluation of the laminate and the laminate was performed in the same manner as in Example 7.
- Example 34 laminate (40). Evaluation of the laminate and the laminate was performed in the same manner as in Example 7.
- a mixed solution (U41) was obtained in the same manner as in Reference Example 1 except that the solid content concentration was changed to 5% by weight.
- a liquid mixture (T41) prepared by the same composition and method as the liquid mixture (T39) of Reference Example 1 was diluted with 542 parts by weight of distilled water and 293 parts by weight of methanol, and then partially neutralized with PAA while stirring. 308 parts by weight of an aqueous solution (concentration: 13% by weight) was quickly added to obtain a mixed solution (U41) having a solid content concentration of 5% by weight.
- Example 1 Using the mixed solution (U41), coating, heat treatment, ionization and drying were performed in the same manner as in Example 1 to obtain a laminate (A41). Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (41). Evaluation of the laminate and laminate was performed in the same manner as in Example 1.
- Comparative Example 2 the mixed liquid (U42) obtained by the same composition and method as the mixed liquid (U41) obtained in Comparative Example 1 was used. Further, coating, heat treatment, ionization and drying were carried out in the same manner as in Example 34 to obtain a laminate (B42).
- Comparative Example 3 and Comparative Example 4 only the compound (A) was used as the compound (L). From these results, it was confirmed that the gas barrier property was low and the hot water resistance was inferior regardless of whether the metal atom of the compound (A) was Al or Ti. That is, it was confirmed that excellent gas barrier properties and hot water resistance were exhibited by using the compound (A) and the compound (B) at a predetermined ratio as the compound (L). In addition, when only the compound (A) was used as the compound (L), the appearance of the pouch deteriorated when the retort treatment was performed under severe conditions.
- a partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in Example 1.
- a liquid mixture (U43) was prepared so that the weight ratio of [inorganic component derived from AIP] / [partially neutralized product of PAA] was 1.0 / 99.0 without adding TMOS and GPTMOS.
- 100 parts by weight of a partially neutralized aqueous solution of PAA (concentration 5% by weight) is quickly added to 2.1 parts by weight of the 9.88% by weight AIP aqueous solution (S43), and the mixed solution (U43) is added. Obtained.
- Example 7 Using the mixed solution (U43), coating, heat treatment, ionization and drying were performed in the same manner as in Example 1 to obtain a laminate (A43). Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (43). Evaluation of the laminate and the laminate was performed in the same manner as in Example 7.
- a partially neutralized aqueous solution of PAA was prepared in the same manner as in Example 1.
- a mixed solution (U44) was prepared so that the weight ratio of [inorganic component derived from titanium lactate] / [partially neutralized product of PAA] was 0.9 / 99.1.
- 1.6 parts by weight of an isopropyl alcohol solution of titanium lactate is added to 100 parts by weight of an aqueous solution of partially neutralized PAA (concentration 5% by weight), and a mixed solution (U44) Got.
- Example 7 Using the mixed solution (U44), coating, heat treatment, ionization and drying were performed in the same manner as in Example 1 to obtain a laminate (A44). Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (44). Evaluation of the laminate and the laminate was performed in the same manner as in Example 7.
- ⁇ Comparative Example 5> The molar ratio of Al / Si was 40.4 / 59.6, and the weight ratio of [inorganic component derived from TMOS and AIP] / [partially neutralized product of PAA] was 40.3 / 59.7.
- a mixed solution (U45) was prepared with the same charging ratio as in Example 3 except for the above. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 461 parts by weight of a 9.88 wt% AIP aqueous solution (S45) was added thereto.
- Example 1 Using the mixed liquid (U45), coating, heat treatment, ionization and drying were performed in the same manner as in Example 1 to obtain a laminate (A45). Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (45). Evaluation of the laminate and laminate was performed in the same manner as in Example 1.
- ⁇ Comparative Example 6> The molar ratio of Al / Si was 0.06 / 99.94, and the weight ratio of [inorganic component derived from TMOS and AIP] / [partially neutralized product of PAA] was 70.0 / 30.0.
- a mixed solution (U46) was prepared with the same charging ratio as in Example 3 except for the above. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 0.4 part by weight of a 9.88 wt% AIP aqueous solution (S46) was added thereto.
- Example 1 Using the mixed solution (U46), coating, heat treatment, ionization and drying were performed in the same manner as in Example 1 to obtain a laminate (A46). Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (46). Evaluation of the laminate and laminate was performed in the same manner as in Example 1.
- TMOS TMOS dissolved in 50 parts by weight of methanol, and 0.4 parts by weight of a 9.88 wt% AIP aqueous solution (S47) was added thereto. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalent, and hydrolysis and condensation reaction was performed at 10 ° C. for 1 hour. And a mixed solution (T47) was obtained.
- S47 9.88 wt% AIP aqueous solution
- Example 1 Using the mixed solution (U47), coating, heat treatment, ionization and drying were performed in the same manner as in Example 1 to obtain a laminate (A47). Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (47). Evaluation of the laminate and laminate was performed in the same manner as in Example 1.
- a laminate (A48) was produced by performing coating and heat treatment in the same manner as in Example 1. This laminate (A48) was not ionized and dried. Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (48). Evaluation of the laminate and laminate was performed in the same manner as in Example 1.
- Table 1 shows the production conditions of the laminates in Examples, Reference Examples, and Comparative Examples.
- Table 3 shows the evaluation results of the laminate.
- the ratio of [number of moles of M 1 derived from compound (A)] / [number of moles of Si atom derived from compound (B)] was 0.1 / 99.9.
- Examples in the range of ⁇ 30.1 / 69.9 (for example, 29.9 / 70.1 and 30.0 / 70.0) exhibited high oxygen barrier properties before and after retorting.
- the oxygen barrier property after the retort treatment was low.
- the oxygen barrier property can be improved by increasing the thickness of the gas barrier layer without adding the compound (A), but in that case, the appearance after the retort treatment deteriorated.
- the gas barrier laminate of the present invention can be effectively used as a packaging material for food, medicine, medical equipment, machine parts, clothing and the like. Among them, it is particularly effective for food packaging applications that require gas barrier properties under high humidity conditions.
- a preferred application of the gas barrier laminate of the present invention includes a retort pouch.
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Abstract
Description
M1X1 mY1 n-m・・・(I)
[式(I)中、M1はAl、Ti、およびZrから選ばれるいずれか1つを表す。X1は、F、Cl、Br、I、OR1、R2COO、R3COCH2COR4、およびNO3から選ばれるいずれか1つを表す。Y1は、F、Cl、Br、I、OR5、R6COO、R7COCH2COR8、NO3およびR9から選ばれるいずれか1つを表す。R1、R2、R5およびR6は、それぞれ独立に、水素原子またはアルキル基を表す。R3、R4、R7、R8およびR9は、それぞれ独立にアルキル基を表す。nはM1の原子価と等しい。mは1~nの整数を表す。]
Si(OR10)pR11 4-p-qX2 q・・・(II)
[式(II)中、R10はアルキル基を表す。R11はアルキル基、アラルキル基、アリール基またはアルケニル基を表す。X2はハロゲン原子を表す。pおよびqは、それぞれ独立に0~4の整数を表す。1≦p+q≦4である。]
M1X1 mY1 n-m・・・(I)
[式(I)中、M1はAl、Ti、およびZrから選ばれるいずれか1つを表す。X1は、F、Cl、Br、I、OR1、R2COO、R3COCH2COR4、およびNO3から選ばれるいずれか1つを表す。Y1は、F、Cl、Br、I、OR5、R6COO、R7COCH2COR8、NO3およびR9から選ばれるいずれか1つを表す。R1、R2、R5およびR6は、それぞれ独立に、水素原子またはアルキル基を表す。R3、R4、R7、R8およびR9は、それぞれ独立にアルキル基を表す。nはM1の原子価と等しい。mは1~nの整数を表す。]
Si(OR10)pR11 4-p-qX2 q・・・(II)
[式(II)中、R10はアルキル基を表す。R11はアルキル基、アラルキル基、アリール基またはアルケニル基を表す。X2はハロゲン原子を表す。pおよびqは、それぞれ独立に0~4の整数を表す。1≦p+q≦4である。]
本発明のガスバリア性積層体は、基材と、基材に積層された少なくとも1つのガスバリア性を有する層とを含む。その層(以下、「ガスバリア層」という場合がある)は、特定の組成物からなる。その組成物は、加水分解性を有する特性基を含有する少なくとも1種の化合物(L)の加水分解縮合物と、カルボキシル基およびカルボン酸無水物基から選ばれる少なくとも1つの官能基を含有する重合体(X)の中和物とを含む。化合物(L)は、加水分解性を有する特性基を含有する少なくとも1種の化合物であり、典型的には、加水分解性を有する特性基が結合した金属原子を含む少なくとも1種の化合物である。化合物(L)は、化合物(A)と、加水分解性を有する特性基が結合したSiを含有する化合物(B)とを含む。以下、重合体(X)に含まれる、カルボキシル基およびカルボン酸無水物基から選ばれる少なくとも1つの官能基を「官能基(F)」という場合がある。官能基(F)に含まれる-COO-基の少なくとも一部が2価以上の金属イオンで中和されている。別の観点では、官能基(F)に含まれる-COO-基が、2価以上の金属イオンと塩を構成している。
ガスバリア層を構成する組成物は、化合物(L)の加水分解縮合物を含む。化合物(L)が加水分解されることによって、化合物(L)の特性基の少なくとも一部が水酸基に置換される。さらに、その加水分解物が縮合することによって、金属原子が酸素を介して結合された化合物が形成される。この縮合が繰り返されると、実質的に金属酸化物とみなしうる化合物が形成される。ここで、この加水分解・縮合が起こるためには、化合物(L)が加水分解性を有する特性基(官能基)を含有していることが重要である。それらの基が結合していない場合、加水分解・縮合反応が起こらないか極めて緩慢になるため、本発明の効果を得ることは困難である。なお、Siは、半金属元素に分類される場合があるが、この明細書では、Siを金属として説明する。
M1X1 mY1 n-m・・・(I)
[式(I)中、M1はAl、Ti、およびZrから選ばれるいずれか1つを表す。X1は、F、Cl、Br、I、OR1、R2COO、R3COCH2COR4、およびNO3から選ばれるいずれか1つを表す。Y1は、F、Cl、Br、I、OR5、R6COO、R7COCH2COR8、NO3およびR9から選ばれるいずれか1つを表す。R1、R2、R5およびR6は、それぞれ独立に、水素原子またはアルキル基を表す。R3、R4、R7、R8およびR9は、それぞれ独立にアルキル基を表す。nはM1の原子価と等しい。mは1~nの整数を表す。]
Si(OR10)pR11 4-p-qX2 q・・・(II)
[式(II)中、R10はアルキル基を表す。R11はアルキル基、アラルキル基、アリール基またはアルケニル基を表す。X2はハロゲン原子を表す。pおよびqは、それぞれ独立に0~4の整数を表す。1≦p+q≦4である。]
Si(OR12)rX3 sZ3 4-r-s・・・(III)
[式(III)中、R12はアルキル基を表す。X3はハロゲン原子を表す。Z3は、カルボキシル基との反応性を有する官能基で置換されたアルキル基を表す。rおよびsは、それぞれ独立に0~3の整数を表す。1≦r+s≦3である。]
ガスバリア層を構成する組成物は、カルボキシル基およびカルボン酸無水物基から選ばれる少なくとも1つの官能基を含有する重合体の中和物を含む。その重合体を、以下、「カルボン酸含有重合体」という場合がある。カルボン酸含有重合体の中和物は、カルボン酸含有重合体の官能基に含まれる-COO-基の少なくとも一部を2価以上の金属イオンで中和することによって得られる。カルボン酸含有重合体は、重合体1分子中に、2個以上のカルボキシル基または1個以上のカルボン酸無水物基を有する。具体的には、アクリル酸単位、メタクリル酸単位、マレイン酸単位、イタコン酸単位などの、カルボキシル基を1個以上有する構成単位を重合体1分子中に2個以上含有する重合体を用いることができる。また、無水マレイン酸単位や無水フタル酸単位などのカルボン酸無水物の構造を有する構成単位を含有する重合体を用いることもできる。カルボキシル基を1個以上有する構成単位および/またはカルボン酸無水物の構造を有する構成単位(以下、両者をまとめて「カルボン酸含有単位(G)」という場合がある)は、1種類または2種類以上がカルボン酸含有重合体に含まれていてもよい。
カルボン酸含有重合体の中和物は、カルボン酸含有重合体のカルボキシル基およびカルボン酸無水物基から選ばれる少なくとも1つの官能基(官能基(F))の少なくとも一部を2価以上の金属イオンで中和することによって得られる。換言すれば、この重合体は、2価以上の金属イオンで中和されたカルボキシル基を含む。
本発明のガスバリア層を構成する組成物は、2つ以上のアミノ基を含有する化合物(P)を含んでもよい。化合物(P)は、化合物(L)および重合体(X)とは異なる化合物である。化合物(P)をさらに含む場合、前記重合体(X)の官能基(F)に含まれる-COO-基の少なくとも一部が、化合物(P)によって中和および/または反応されている状態となる。化合物(P)として、アルキレンジアミン類、ポリアルキレンポリアミン類、脂環族ポリアミン類、芳香族ポリアミン類、ポリビニルアミン類等を用いることができるが、ガスバリア性積層体のガスバリア性がより良好となる観点から、アルキレンジアミンが好ましい。
本発明のガスバリア層を構成する組成物は、2つ以上の水酸基を含有する化合物(Q)を含んでもよい。化合物(Q)をさらに含む場合、前記重合体(X)の官能基(F)に含まれる-COO-基の少なくとも一部が、化合物(Q)によって反応してエステル結合を形成している状態となる。この構成によれば、ガスバリア性積層体の、伸長後のガスバリア性が向上する。より具体的には、化合物(Q)を添加することによって、ガスバリア性積層体が伸長されてもガスバリア層がダメージを受けにくくなる。その結果、伸長された後でも高いガスバリア性が保持される。たとえば、印刷やラミネートなどの加工時のテンションによる伸長や、食品が充填された袋が落下した時の伸長などが起きた後の状態においても、ガスバリア性積層体のガスバリア性が低下しにくくなる。
本発明のガスバリア性積層体を構成する基材としては、様々な材料からなる基材を用いることができる。たとえば、熱可塑性樹脂フィルムや熱硬化性樹脂フィルムといったフィルム;布帛や紙類等の繊維集合体;木材;金属酸化物や金属などからなる所定形状のフィルムを用いることができる。中でも、熱可塑性樹脂フィルムは、食品包装材料に用いられるガスバリア性積層体の基材として特に有用である。また、基材は紙層を含んでもよい。紙層を含む基材を用いることによって、紙容器用の積層体が得られる。なお、基材は複数の材料からなる多層構成のものであってもよい。
(1)ガスバリア層/ポリエステル/ポリアミド/ポリオレフィン、
(2)ガスバリア層/ポリエステル/ガスバリア層/ポリアミド/ポリオレフィン、
(3)ポリエステル/ガスバリア層/ポリアミド/ポリオレフィン、
(4)ガスバリア層/ポリアミド/ポリエステル/ポリオレフィン、
(5)ガスバリア層/ポリアミド/ガスバリア層/ポリエステル/ポリオレフィン、
(6)ポリアミド/ガスバリア層/ポリエステル/ポリオレフィン、
(7)ガスバリア層/ポリオレフィン/ポリアミド/ポリオレフィン、
(8)ガスバリア層/ポリオレフィン/ガスバリア層/ポリアミド/ポリオレフィン、
(9)ポリオレフィン/ガスバリア層/ポリアミド/ポリオレフィン、
(10)ガスバリア層/ポリオレフィン/ポリオレフィン、
(11)ガスバリア層/ポリオレフィン/ガスバリア層/ポリオレフィン、
(12)ポリオレフィン/ガスバリア層/ポリオレフィン、
(13)ガスバリア層/ポリエステル/ポリオレフィン、
(14)ガスバリア層/ポリエステル/ガスバリア層/ポリオレフィン、
(15)ポリエステル/ガスバリア層/ポリオレフィン、
(16)ガスバリア層/ポリアミド/ポリオレフィン、
(17)ガスバリア層/ポリアミド/ガスバリア層/ポリオレフィン、
(18)ポリアミド/ガスバリア層/ポリオレフィン、
(19)ガスバリア/ポリエステル/紙、
(20)ガスバリア層/ポリアミド/紙、
(21)ガスバリア層/ポリオレフィン/紙、
(22)ポリエチレン(PE)層/紙層/PE層/ガスバリア層/ポリエチレンテレフタレート(PET)層/PE層、
(23)ポリエチレン(PE)層/紙層/PE層/ガスバリア層/ポリアミド層/PE層、
(24)PE層/紙層/PE層/ガスバリア層/PE、
(25)紙層/PE層/ガスバリア層/PET層/PE層、
(26)PE層/紙層/ガスバリア層/PE層、
(27)紙層/ガスバリア層/PET層/PE層、
(28)紙層/ガスバリア層/PE層、
(29)ガスバリア層/紙層/PE層、
(30)ガスバリア層/PET層/紙層/PE層、
(31)PE層/紙層/PE層/ガスバリア層/PE層/水酸基含有ポリマー層、
(32)PE層/紙層/PE層/ガスバリア層/PE層/ポリアミド層、
(33)PE層/紙層/PE層/ガスバリア層/PE層/ポリエステル層。
以下、本発明のガスバリア性積層体を製造するための方法について説明する。この方法によれば、本発明のガスバリア性積層体を容易に製造できる。本発明の製造方法に用いられる材料、および積層体の構成は、上述したものと同様であるので、重複する部分については説明を省略する場合がある。
(i-a)化合物(A)および化合物(A)の部分加水分解縮合物から選ばれる少なくとも1種の化合物と、カルボキシル基を含有し分子量が100以下である化合物(D)と、を含む溶液(S)を調製する工程と、
(i-b)化合物(B)および化合物(B)の部分加水分解縮合物から選ばれる少なくとも1種の化合物と溶液(S)とを混合することによって溶液(T)を調製する工程と、
(i-c)溶液(T)中において、化合物(A)と化合物(B)とを含む複数の化合物(L)の加水分解縮合物(オリゴマー(V))を形成する工程と、
(i-d)上記(i-c)の工程を経た溶液(T)と重合体(X)とを混合することによって溶液(U)を調製する工程と、
(i-e)溶液(U)を基材に塗工して乾燥させることによって層を形成する工程と、を含むことが極めて好ましい。
酸素透過量測定装置(モダンコントロール社製「MOCON OX-TRAN2/20」)を用いて酸素透過度を測定した。温度20℃、酸素圧1気圧、キャリアガス圧力1気圧の条件下で、酸素透過度(単位:cc/m2/day/atm)を測定した(cc=cm3)。キャリアガスとしては2体積%の水素ガスを含む窒素ガスを使用した。このとき、湿度を85%RHとし、酸素供給側とキャリアガス側とを同一の湿度とした。基材の片面のみにガスバリア層を形成した積層体については、酸素供給側にガスバリア層が向きキャリアガス側に基材が向くように積層体をセットした。
まず、積層体を30cm×21cmに切り出した。次に、切り出した積層体を、23℃、50%RHの条件で手動伸長装置を用いて10%伸長し、伸長状態で5分間保持した。その後、上記と同様の手法で酸素透過度を測定した。
積層体を温度20℃、湿度65%RHの条件下で24時間調湿を行った。その後、自動接触角計(協和界面科学製、DM500)を用いて、温度20℃、湿度65%RHの条件で2μLの水をガスバリア層上に滴下した。そして、日本工業規格(JIS)-R3257に準拠した方法で、ガスバリア層と水との接触角を測定した。
積層体を温度23℃、湿度50%RHの条件下で24時間調湿を行った。その後、積層体を、MD方向およびTD方向に対して15cm×15mmに切り出した。切り出した積層体について、温度23℃、湿度50%RHの条件で、JIS-K7127に準拠した方法によって、引っ張り強伸度およびヤング率を測定した。
積層体を10cm×10cmに切り出し、MDおよびTDにおける長さをノギスで測定した。この積層体を、乾燥機中において80℃で5分間加熱し、加熱後のMDおよびTDにおける長さを測定した。そして、以下の式から乾熱収縮率(%)を測定した。
乾熱収縮率(%)=(lb-la)×100/lb
[式中、lbは加熱前の長さを表す。laは加熱後の長さを表す。]
[FT-IRによるイオン化度の算出]
数平均分子量150,000のポリアクリル酸を蒸留水に溶解し、所定量の水酸化ナトリウムでカルボキシル基を中和した。得られたポリアクリル酸の中和物の水溶液を、基材上に、イオン化度の測定の対象となる積層体のガスバリア層と同じ厚さになるようにコートし、乾燥させた。基材には、2液型のアンカーコート剤(三井武田ケミカル株式会社製、タケラック626(商品名)およびタケネートA50(商品名)、以下「AC」と略記することがある)を表面にコートした延伸ナイロンフィルム(ユニチカ株式会社製、エンブレム ON-BC(商品名)、厚さ15μm、以下「ON」と略記することがある)を用いた。このようにして、カルボキシル基の中和度が、0、25、50、75、80、90モル%の標準サンプル[積層体(ポリアクリル酸の中和物からなる層/AC/ON)]を作製した。これらのサンプルについて、フーリエ変換赤外分光光度計(Perkin Elmer製、Spectrum One)を用いて、ATR(全反射測定)のモードで、赤外吸収スペクトルを測定した。そして、ポリアクリル酸の中和物からなる層に含まれるC=O伸縮振動に対応する2つのピーク、すなわち、1600cm-1~1850cm-1の範囲に観察されるピークと1500cm-1~1600cm-1の範囲に観察されるピークとについて、吸光度の最大値の比を算出した。そして、算出した比と、各標準サンプルのイオン化度とを用いて検量線1を作成した。
基材として前述したONを用いた積層体について、FT-IRの測定よりイオン化度の異なる標準サンプルを作製した。具体的には、イオン化度(イオン:カルシウムイオン)が0~100モル%間で約10モル%ずつ異なる11種類の標準サンプルを作製した。各々のサンプルについて、波長分散型蛍光X線装置(株式会社リガク製、ZSXminiII)を用いて、カルシウム元素の蛍光X線強度を測定し、予めFT-IRで測定したイオン化度から検量線2を作成した。得られた検量線2を用いて、各種条件で作製した積層体のカルシウムイオン化度を算出した。
上述した方法によって、化合物(L)に由来する無機成分の重量、および、化合物(L)に由来する有機成分の重量と重合体(X)に由来する有機成分の重量との合計を算出した。
ラミネート体(サイズ:12cm×12cm)を2枚作製した。そして、その2枚を、無延伸ポリプロピレンフィルム(トーセロ株式会社製、RXC-18(商品名)、厚さ50μm、以下「CPP」と略記することがある)が内側になるように重ねあわせたのち、ラミネート体の3辺をその端から5mmまでヒートシールした。ヒートシールされた2枚のラミネート体の間に蒸留水80gを注入したのち、残された第4辺を同様にヒートシールした。このようにして、蒸留水が中に入ったパウチを作製した。
まず、レトルト処理後の酸素バリア性の測定で用いたパウチと同様のパウチを作製した。このパウチを、135℃、60分、0.25MPaの条件でレトルト処理を行った。レトルト処理後、加熱を停止し、内部温度が60℃になった時点で、レトルト処理装置からパウチを取り出し、20℃、65%RHの室内でパウチを1時間放置した。その後外観観察を行い、レトルト前と同様に曇りがない場合を「非常に良好(S)」、やや曇りがあるが実用上問題がない場合は「良好(A)」、レトルト前と比べ明らかに曇りがある場合については「不良(B)」と判定した。
数平均分子量150,000のポリアクリル酸(PAA)を蒸留水で溶解し、水溶液中の固形分濃度が13重量%であるPAA水溶液を得た。続いて、このPAA水溶液に、13%アンモニア水溶液を加え、PAAのカルボキシル基の1モル%を中和して、PAAの部分中和水溶液を得た。
PAAの部分中和物水溶液およびAIP水溶液は、実施例1と同様に調製した。そして、Al/Siのモル比が30.1/69.9、[TMOSおよびAIPに由来する無機成分]/[PAAの部分中和物]の重量比が25.5/74.5となるように混合液(U2)を調製した。具体的には、まず、TMOS50重量部をメタノール50重量部に溶解し、これに9.88重量%のAIP水溶液(S2)を293重量部加えた。さらに、TMOSに対する水の割合が1.95モル当量となるよう蒸留水を3.3重量部と0.1Nの塩酸8.2重量部とを加え、10℃で1時間、加水分解および縮合反応を行い、混合液(T2)を得た。続いて、得られた混合液(T2)を蒸留水850重量部、メタノール405重量部で希釈した後、攪拌しながらPAAの部分中和物水溶液(濃度13重量%)607重量部を速やかに添加し、固形分濃度5重量%の混合液(U2)を得た。
PAAの部分中和物水溶液およびAIP水溶液は、実施例1と同様に調製した。そして、反応時間のみを変えて、混合液(U3)を調製した。
AIPをチタンテトライソプロポキシド(TIP)に変更し、混合液(U4)を調製した。具体的には、酢酸1200重量部と蒸留水1800重量部を混合し、この酢酸水溶液にTIP284重量部(TIP/酢酸/蒸留水=1/20/100(モル比))を撹拌しながら加え、その後80℃で1時間加熱することで濃度が8.6重量%のTIP水溶液(S4)を得た。続いて、TMOS50重量部をメタノール50重量部に溶解し、これにTIP水溶液(S4)を13.5重量部加えた。さらに、TMOSに対する水の割合が1.95モル当量となるよう蒸留水を3.3重量部と0.1Nの塩酸8.2重量部とを加え、10℃で5時間、加水分解および縮合反応を行い、混合液(T4)を得た。続いて、実施例1と同様の組成および方法で、固形分濃度5重量%の混合液(U4)を得た。
AIPをジルコニウムテトライソプロポキシド(ZIP)に変更し、混合液(U5)を調製した。具体的には、酢酸1200重量部と蒸留水1800重量部を混合し、この酢酸水溶液にZIP327重量部(ZIP/酢酸/蒸留水=1/20/100(モル比))を撹拌しながら加え、その後80℃で1時間加熱することで濃度が9.8重量%のZIP水溶液(S5)を得た。次に、TMOS50重量部をメタノール50重量部に溶解し、これに上記9.8重量%ZIP水溶液(S5)を13.6重量部加えた。さらに、TMOSに対する水の割合が1.95モル当量となるよう蒸留水を3.3重量部と0.1Nの塩酸8.2重量部とを加え、10℃で5時間、加水分解および縮合反応を行い、混合液(T5)を得た。続いて、実施例1と同様の組成および方法で固形分濃度5重量%の混合液(U5)を得た。
PAAの部分中和物水溶液およびAIP水溶液は、実施例1と同様に調製した。そして[TMOSおよびAIPに由来する無機成分]/[PAAの部分中和物]の重量比が30.2/69.8となるようにした以外は実施例3と同様の仕込み比で、混合液(U6)を調製した。具体的には、まず、実施例3で得られた混合液(T3)と同様の組成および方法で混合液(T6)を調製した。この混合液(T6)を、蒸留水567重量部およびメタノール283重量部で希釈した後、攪拌しながらPAAの部分中和物水溶液(濃度13重量%)354重量部を速やかに添加し、固形分濃度が5重量%の混合液(U6)を得た。
PAAの部分中和物水溶液およびAIP水溶液は、実施例1と同様に調製した。そしてAl/Siのモル比が1.9/98.1となるようにした以外は実施例6と同様の仕込み比で混合液(U7)を調製した。具体的には、まず、TMOS50重量部をメタノール50重量部に溶解し、これに9.88重量%AIP水溶液(S7)を13.2重量部加えた。さらに、TMOSに対する水の割合が1.95モル当量となるよう蒸留水を3.3重量部と0.1Nの塩酸8.2重量部とを加え、10℃で5時間、加水分解および縮合反応を行い、混合液(T7)を得た。続いて、実施例6と同様の組成および方法で固形分濃度が5重量%の混合液(U7)を得た。
PAAの部分中和物水溶液およびAIP水溶液は、実施例1と同様に調製した。そしてAl/Siのモル比が2.8/97.2となるようにした以外は実施例6と同様の仕込み比で混合液(U8)を調製した。具体的には、まず、TMOS50重量部をメタノール50重量部に溶解し、これに9.88重量%AIP水溶液(S8)を19.8重量部加えた。さらに、TMOSに対する水の割合が1.95モル当量となるよう蒸留水を3.3重量部と0.1Nの塩酸8.2重量部とを加え、10℃で5時間、加水分解および縮合反応を行い、混合液(T8)を得た。続いて、実施例6と同様の組成、方法で固形分濃度が5重量%の混合液(U8)を得た。
PAAの部分中和物水溶液およびAIP水溶液は、実施例1と同様に調製した。そして実施例2と同様の仕込み比、すなわちAl/Siのモル比が30/70、[TMOSおよびAIPに由来する無機成分]/[PAAの部分中和物]の重量比が25.5/74.5となるように混合液(U9)を調製した。具体的には、まず、TMOS50重量部をメタノール50重量部に溶解し、これに9.88重量%AIP水溶液(S9)を293重量部加えた。さらに、TMOSに対する水の割合が1.95モル当量となるよう蒸留水を3.3重量部と0.1Nの塩酸8.2重量部とを加え、10℃で5時間、加水分解および縮合反応を行い、混合液(T9)を得た。続いて、得られた混合液(T9)を蒸留水850重量部、メタノール405重量部で希釈した後、攪拌しながらPAAの部分中和物水溶液(濃度13重量%)607重量部を速やかに添加し、固形分濃度が5重量%の混合液(U9)を得た。
PAAの部分中和物水溶液およびAIP水溶液は、実施例1と同様に調製した。そしてAl/Siのモル比が0.1/99.9、[TMOSおよびAIPに由来する無機成分]/[PAAの部分中和物]の重量比が80.0/20.0となるように混合液(U10)を調製した。具体的には、まず、TMOS50重量部をメタノール50重量部に溶解し、これに9.88重量%AIP水溶液(S10)を0.7重量部加えた。さらに、TMOSに対する水の割合が1.95モル当量となるよう蒸留水を3.3重量部と0.1Nの塩酸8.2重量部とを加え、10℃で5時間、加水分解および縮合反応を行い、混合液(T10)を得た。続いて、混合液(T10)を、蒸留水212重量部およびメタノール131重量部で希釈した後、攪拌しながらPAAの部分中和物の水溶液(濃度13重量%)38重量部を速やかに添加し、固形分濃度が5重量%の混合液(U10)を得た。
PAAの部分中和物水溶液およびAIP水溶液は、実施例1と同様に調製した。そしてAl/Siのモル比が29.9/70.1、[TMOSおよびAIPに由来する無機成分]/[PAAの部分中和物]の重量比が36.9/63.1となるように混合液(U11)を調製した。具体的には、まず、TMOS50重量部をメタノール50重量部に溶解し、これに9.88重量%AIP水溶液(S11)を290重量部加えた。さらに、TMOSに対する水の割合が1.95モル当量となるよう蒸留水を3.3重量部と0.1Nの塩酸8.2重量部とを加え、10℃で5時間、加水分解および縮合反応を行い、混合液(T11)を得た。続いて、混合液(T11)を、蒸留水567重量部およびメタノール283重量部で希釈した後、攪拌しながらPAAの部分中和物水溶液(濃度13重量%)354重量部を速やかに添加し、固形分濃度が5重量%の混合液(U11)を得た。
PAAの部分中和物水溶液およびAIP水溶液は、実施例1と同様に調製した。そしてAl/Siのモル比が0.1/99.9、[TMOSおよびAIPに由来する無機成分]/[PAAの部分中和物]の重量比が70.0/30.0となるように混合液(U12)を調製した。具体的には、まず、TMOS50重量部をメタノール50重量部に溶解し、これに9.88重量%AIP水溶液(S12)を0.7重量部加えた。さらに、TMOSに対する水の割合が1.95モル当量となるよう蒸留水を3.3重量部と0.1Nの塩酸8.2重量部とを加え、10℃で5時間、加水分解および縮合反応を行い、混合液(T12)を得た。続いて、混合液(T12)を、蒸留水243重量部およびメタノール144重量部で希釈した後、攪拌しながらPAAの部分中和物の水溶液(濃度13重量%)65重量部を速やかに添加し、固形分濃度が5重量%の混合液(U12)を得た。
PAAの部分中和物水溶液およびAIP水溶液は、実施例1と同様に調製した。そしてAl/Siのモル比が3.0/97.0、[TMOSおよびAIPに由来する無機成分]/[PAAの部分中和物]の重量比が20.0/80.0となるように混合液(U13)を調製した。具体的には、まず、TMOS50重量部をメタノール50重量部に溶解し、これに9.88重量%AIP水溶液(S13)20.8重量部加えた。さらに、TMOSに対する水の割合が1.95モル当量となるよう蒸留水を3.3重量部と0.1Nの塩酸8.2重量部とを加え、10℃で5時間、加水分解および縮合反応を行い、混合液(T13)を得た。続いて、混合液(T13)を、蒸留水868重量部およびメタノール412重量部で希釈した後、攪拌しながらPAAの部分中和物水溶液(濃度13重量%)623重量部を速やかに添加し、固形分濃度が5重量%の混合液(U13)を得た。
PAAの部分中和物水溶液およびAIP水溶液は、実施例1と同様に調製した。そしてAl/Siのモル比が3.0/97.0、[TMOSおよびAIPに由来する無機成分]/[PAAの部分中和物]の重量比が80.0/20.0となるように混合液(U14)を調製した。具体的には、まず、TMOS50重量部をメタノール50重量部に溶解し、これに9.88重量%AIP水溶液(S14)21.0重量部加えた。さらに、TMOSに対する水の割合が1.95モル当量となるよう蒸留水を3.3重量部と0.1Nの塩酸8.2重量部とを加え、10℃で5時間、加水分解および縮合反応を行い、混合液(T14)を得た。続いて、混合液(T14)を、蒸留水214重量部およびメタノール132重量部で希釈した後、攪拌しながらPAAの部分中和物水溶液(濃度13重量%)39重量部を速やかに添加し、固形分濃度が5重量%の混合液(U14)を得た。
PAAの部分中和物水溶液およびAIP水溶液は、実施例1と同様に調製した。そしてAl/Siのモル比が3.0/97.0、[TMOSおよびAIPに由来する無機成分]/[PAAの部分中和物]の重量比が70.0/30.0となるように混合液(U15)を調製した。具体的には、まず、TMOS50重量部をメタノール50重量部に溶解し、これに9.88重量%AIP水溶液(S15)21.1重量部加えた。さらに、TMOSに対する水の割合が1.95モル当量となるよう蒸留水を3.3重量部と0.1Nの塩酸8.2重量部とを加え、10℃で5時間、加水分解および縮合反応を行い、混合液(T15)を得た。続いて、混合液(T15)を、蒸留水245重量部およびメタノール145重量部で希釈した後、攪拌しながらPAAの部分中和物水溶液(濃度13重量%)67重量部を速やかに添加し、固形分濃度が5重量%の混合液(U15)を得た。
PAAの部分中和物水溶液およびAIP水溶液は、実施例1と同様に調製した。そしてAl/Siのモル比が2.9/97.1、[TMOSおよびAIPに由来する無機成分]/[PAAの部分中和物]の重量比が10.2/89.8となるように混合液(U16)を調製した。具体的には、まず、TMOS50重量部をメタノール50重量部に溶解し、これに9.88重量%AIP水溶液(S16)20.3重量部加えた。さらに、TMOSに対する水の割合が1.95モル当量となるよう蒸留水を3.3重量部と0.1Nの塩酸8.2重量部とを加え、10℃で5時間、加水分解および縮合反応を行い、混合液(T16)を得た。続いて、混合液(T16)を、蒸留水1700重量部およびメタノール769重量部で希釈した後、攪拌しながらPAAの部分中和物水溶液(濃度13重量%)1366重量部を速やかに添加し、固形分濃度が5重量%の混合液(U13)を得た。
PAAの部分中和物水溶液およびAIP水溶液は、実施例1と同様に調製した。そしてAl/Siのモル比が3.0/97.0、[TMOSおよびAIPに由来する無機成分]/[PAAの部分中和物]の重量比が90.2/9.8となるように混合液(U17)を調製した。具体的には、まず、TMOS50重量部をメタノール50重量部に溶解し、これに9.88重量%AIP水溶液(S17)21.3重量部加えた。さらに、TMOSに対する水の割合が1.95モル当量となるよう蒸留水を3.3重量部と0.1Nの塩酸8.2重量部とを加え、10℃で5時間、加水分解および縮合反応を行い、混合液(T17)を得た。続いて、混合液(T17)を、蒸留水189重量部およびメタノール121重量部で希釈した後、攪拌しながらPAAの部分中和物水溶液(濃度13重量%)17重量部を速やかに添加し、固形分濃度が5重量%の混合液(U17)を得た。
PAAの部分中和物水溶液およびAIP水溶液は、実施例1と同様に調製した。続いて、TMOS/γ-グリシドキシドキシプロピルトリメトキシシラン(GPTMOS)のモル比が99.5/0.5、Al/Siのモル比が2.8/97.2、[TMOS、AIPおよびGPTMOSに由来する無機成分]/[GPTMOSの有機成分とPAAの部分中和物]の重量比が30.5/69.5となるように混合液(U18)を調製した。具体的には、まず、TMOS49.6重量部、GPTMOS0.4重量部をメタノール50重量部に溶解し、これに実施例1と同様の方法で調製した9.88重量%AIP水溶液(S18)を19.6重量部加えた。さらに、TMOSおよびGPTMOSの合計に対する水の割合が1.95モル当量となるよう蒸留水を3.3重量部と0.1Nの塩酸8.2重量部とを加え、10℃で5時間、加水分解および縮合反応を行い、混合液(T18)を得た。続いて、混合液(T18)を、蒸留水566重量部およびメタノール283重量部で希釈した後、攪拌しながら、PAAの部分中和物の水溶液(濃度13重量%)352重量部を速やかに添加し、固形分濃度が5重量%の混合液(U18)を得た。
TMOS/GPTMOSのモル比が80.0/20.0となるようにした以外は実施例18と同様の仕込み比で混合液(U19)を得た。具体的には、まず、TMOS36.0重量部、GPTMOS14.0重量部をメタノール50重量部に溶解し、これに9.88重量%AIP水溶液(S19)を19.8重量部加えた。さらに、TMOSおよびGPTMOSの合計に対する水の割合が1.95モル当量となるよう蒸留水を3.0重量部と0.1Nの塩酸7.4重量部とを加え、10℃で5時間、加水分解および縮合反応を行い、混合液(T19)を得た。続いて、混合液(T19)を、蒸留水520重量部およびメタノール302重量部で希釈した後、攪拌しながらPAAの部分中和物水溶液(濃度13重量%)267重量部を速やかに添加し、固形分濃度が5重量%の混合液(U19)を得た。
PAAの部分中和物水溶液およびAIP水溶液は、実施例1と同様に調製した。続いて、TMOS/GPTMOSのモル比が89.9/10.1、Al/Siのモル比が3.1/96.9、[TMOS、AIPおよびGPTMOSに由来する無機成分]/[GPTMOSの有機成分とPAAの部分中和物]の重量比が31.5/68.5となるように混合液(U20)を調製した。具体的には、まず、TMOS42.6重量部、GPTMOS7.4重量部をメタノール50重量部に溶解し、これに9.88重量%AIP水溶液(S20)を20.6重量部加えた。さらに、TMOSおよびGPTMOSの合計に対する水の割合が1.95モル当量となるよう蒸留水を3.2重量部と0.1Nの塩酸7.8重量部とを加え、10℃で5時間、加水分解および縮合反応を行い、混合液(T20)を得た。続いて、混合液(T20)を、蒸留水542重量部およびメタノール302重量部で希釈した後、攪拌しながらPAAの部分中和物の水溶液(濃度13重量%)293重量部を速やかに添加し、固形分濃度が5重量%の混合液(U20)を得た。
TMOSとGPTMOSのモル比が98.0/2.0となるようにした以外は実施例18と同様の仕込み比で混合液(U21)を得た。具体的には、まず、TMOS48.5重量部、GPTMOS1.5重量部をメタノール50重量部に溶解し、これに9.88重量%AIP水溶液(S21)を19.2重量部加えた。さらに、TMOSおよびGPTMOSの合計に対する水の割合が1.95モル当量となるよう蒸留水を3.3重量部と0.1Nの塩酸8.1重量部とを加え、10℃で5時間、加水分解および縮合反応を行い、混合液(T21)を得た。続いて、続いて、混合液(T21)を、蒸留水562重量部およびメタノール285重量部で希釈した後、攪拌しながらPAAの部分中和物水溶液(濃度13重量%)345重量部を速やかに添加し、固形分濃度が5重量%の混合液(U21)を得た。
TMOS/GPTMOSのモル比が99.9/0.1となるようにした以外は実施例18と同様の仕込み比で混合液(U22)を得た。具体的には、まず、TMOS49.9重量部、GPTMOS0.1重量部をメタノール50重量部に溶解し、これに9.88重量%AIP水溶液(S22)を21.0重量部加えた。さらに、TMOSおよびGPTMOSの合計に対する水の割合が1.95モル当量となるよう蒸留水を3.3重量部と0.1Nの塩酸8.1重量部とを加え、10℃で5時間、加水分解および縮合反応を行い、混合液(T22)を得た。続いて、混合液(T22)を、蒸留水567重量部およびメタノール283重量部で希釈した後、攪拌しながらPAAの部分中和物の水溶液(濃度13重量%)354重量部を速やかに添加し、固形分濃度が5重量%の混合液(U22)を得た。
TMOS/GPTMOSのモル比が70.0/30.0となるようにした以外は実施例18と同様の仕込み比で混合液(U23)を得た。具体的には、まず、TMOS30.0重量部、GPTMOS20.0重量部をメタノール50重量部に溶解し、これに9.88重量%AIP水溶液(S23)を17.9重量部加えた。さらにTMOSおよびGPTMOSの合計に対する水の割合が1.95モル当量となるよう蒸留水を2.9重量部と0.1Nの塩酸7.0重量部とを加え、10℃で5時間、加水分解および縮合反応を行い、混合液(T23)を得た。続いて、混合液(T23)を、蒸留水500重量部およびメタノール310重量部で希釈した後、攪拌しながらPAAの部分中和物水溶液(濃度13重量%)229重量部を速やかに添加し、固形分濃度5重量%の混合液(U23)を得た。
実施例24では、実施例21で得られた混合液(U21)と同様の組成および方法で得た混合液(U24)を使用した。また、実施例1と同様にコートおよび熱処理を行って積層体を作製した。この積層体を、0.1重量%の酢酸カルシウム水溶液(85℃)に12秒間浸漬してイオン化した後、実施例1と同様に乾燥を行い、積層体(A24)を得た。
実施例25では、実施例21で得られた混合液(U21)と同様の組成および方法で得た混合液(U25)を使用した。また、実施例1と同様にコートおよび熱処理を行って積層体を作製した。この積層体を、0.2重量%の酢酸カルシウム水溶液(85℃)に6秒間浸漬してイオン化した後、実施例1と同様に乾燥を行い、積層体(A25)を得た。
実施例26では、実施例21で得られた混合液(U21)と同様の組成および方法で得た混合液(U26)を使用した。また、実施例1と同様にコートおよび熱処理を行って積層体を作製した。この積層体を、0.2重量%の酢酸カルシウム水溶液(85℃)に12秒間浸漬してイオン化した後、実施例1と同様に乾燥を行い、積層体(A26)を得た。
実施例27では、実施例21で得られた混合液(U21)と同様の組成および方法で得た混合液(U27)を使用した。また、実施例1と同様にコートおよび熱処理を行って積層体を作製した。この積層体を、2重量%の酢酸マグネシウム水溶液(85℃)に12秒間浸漬してイオン化した後、実施例1と同様に乾燥を行い、積層体(A27)を得た。
実施例28では、実施例21で得られた混合液(U21)と同様の組成および方法で得た混合液(U28)を使用した。また、実施例1と同様にコートおよび熱処理を行って積層体を得た。この積層体を、2重量%の酢酸亜鉛水溶液(85℃)に12秒間浸漬してイオン化した後、実施例1と同様に乾燥を行い、積層体(A28)を得た。
PAAの部分中和物水溶液およびAIP水溶液は、実施例1と同様に調製した。一方、エチレンジアミン(EDA)/HClのモル比が1/2となるようにEDAを1N塩酸に溶解させ、EDA塩酸塩水溶液を得た。[EDAのアミノ基]/[PAAのカルボキシル基]の当量比が1.9/100となるようにEDA塩酸塩水溶液を加えた以外は、実施例7と同様の仕込み比で、混合液(U29)を調製した。具体的には、まず、実施例7の混合液(T7)と同様の組成および方法で調製した混合液(T29)を、蒸留水567重量部およびメタノール283重量部で希釈した後、攪拌しながらPAAの部分中和物水溶液(濃度13重量%)354重量部を速やかに添加し、更にEDA塩酸塩水溶液12.7重量部を加え、固形分濃度5重量%の混合液(U29)を得た。
PAAの部分中和物水溶液およびAIP水溶液は、実施例1と同様に調製した。一方、濃度が10重量%となるようにポリビニルアルコール(株式会社クラレ製、PVA117、以下「PVA」と略記する場合がある)を蒸留水に加え、85℃で3時間加熱することによってPVA水溶液を得た。
AIP水溶液調製時の酸をプロピオン酸にした以外は、実施例21と同様の仕込み比で混合液(U31)を調製した。具体的には、プロピオン酸74重量部と蒸留水1800重量部を混合した後、このプロピオン酸水溶液にAIP204重量部(AIP/プロピオン酸/蒸留水=1/1/100(モル比))を撹拌しながら加え、その後80℃で1時間加熱することで濃度が9.82重量%のAIP水溶液(S31)を得た。このAIP水溶液(S31)を用いた以外は実施例18の混合液(U21)と同様の組成および方法で、混合液(U31)を得た。
AIP水溶液調製時の酸をヘキサン酸にした以外は、実施例21と同様の仕込み比で混合液(U32)を調製した。具体的には、ヘキサン酸116重量部と蒸留水1800重量部を混合した後、このヘキサン酸水溶液にAIP204重量部(AIP/ヘキサン酸/蒸留水=1/1/100(モル比))を撹拌しながら加え、その後80℃で1時間加熱することで濃度が9.62重量%のAIP水溶液(S32)を得た。このAIP水溶液(S32)を用いた以外は実施例21の混合液(U21)と同様の組成および方法で、混合液(U32)を得た。
実施例33では、実施例21で得られた混合液(U21)と同様の組成および方法で得た混合液(U33)を使用した。基材の片面のみにガスバリア層を形成したこと以外は実施例1と同様にコート、熱処理、イオン化、乾燥を行い、積層体(A33)を得た。
実施例34では、実施例8で得られた混合液(U8)と同様の組成および方法で得た混合液(U34)を使用した。また、基材を延伸ナイロンフィルム(上述した「ON」)にした以外は実施例1と同様にコート、熱処理、イオン化、乾燥を行い、積層体(B34)を得た。
実施例35では、実施例21で得られた混合液(U21)と同様の組成および方法で得た混合液(U35)を使用した。また、実施例34と同様にコート、熱処理、イオン化、乾燥を行い、積層体(B35)を得た。
実施例36では、実施例8で得られた混合液(U8)と同様の組成および方法で得た混合液(U36)を使用した。また、実施例34と同様にコート、熱処理、イオン化、乾燥を行い、積層体(B36)を得た。
実施例37では、実施例21で得られた混合液(U21)と同様の組成および方法で得た混合液(U37)を使用した。また、実施例34と同様にコート、熱処理、イオン化、乾燥を行い、積層体(B37)を得た。
実施例38では、実施例21で得られた混合液(U21)と同様の組成、方法で得た混合液(U38)を使用した。また、基材の片面のみにガスバリア層を形成したこと以外は実施例34と同様にコート、熱処理、イオン化、乾燥を行い、積層体(B38)を得た。
参考例1では、TMOS/GPTMOSのモル比が89.9/10.1、[TMOSとGPTMOSに由来する無機成分]/[GPTMOSの有機成分とPAAの部分中和物]の重量比が31.5/68.5となるように、混合液(T39)を調製した。具体的には、まず、TMOS46重量部およびGPTMOS8重量部を、メタノール50重量部に溶解した。これにTMOSとGPTMOSの合計に対する水の割合が1.95モル当量でpHが2以下となるよう、蒸留水3.2重量部と0.1Nの塩酸7.8重量部とを加え、10℃で5時間、加水分解および縮合反応を行い、混合液(T39)を得た。
参考例2では、参考例1で得られた混合液(U39)と同様の組成および方法で得た混合液(U40)を使用した。また、基材をONにした以外は、実施例1と同様にコート、熱処理、イオン化、乾燥を行い、積層体(B40)を得た。
本発明の実施例等で用いた延伸ポリエチレンテレフタレートフィルム(「PET」;東レ株式会社製、ルミラーP60(商品名)、厚さ12μm)の性能を示した。
本発明の実施例等で用いた延伸ナイロンフィルム(「ON」;ユニチカ株式会社製、エンブレムON-BC(商品名)、厚さ15μm)の性能を示した。
固形分濃度を5重量%にした以外は、参考例1と同様に混合液(U41)を得た。まず、参考例1の混合液(T39)と同様の組成および方法で調製した混合液(T41)を蒸留水542重量部、メタノール293重量部で希釈した後、攪拌しながらPAAの部分中和物の水溶液(濃度13重量%)308重量部を速やかに添加し、固形分濃度5重量%の混合液(U41)を得た。
比較例2では、比較例1で得られた混合液(U41)と同様の組成および方法で得た混合液(U42)を使用した。また、実施例34と同様にコート、熱処理、イオン化、乾燥を行い、積層体(B42)を得た。
PAAの部分中和物水溶液およびAIP水溶液は、実施例1と同様に調製した。TMOS、GPTMOSは加えずに[AIPに由来する無機成分]/[PAAの部分中和物]の重量比が1.0/99.0となるように、混合液(U43)を調製した。具体的には、9.88重量%AIP水溶液(S43)2.1重量部に、PAAの部分中和物水溶液(濃度5重量%)100重量部を速やかに添加し、混合液(U43)を得た。
PAAの部分中和物水溶液は、実施例1と同様に調製した。[チタンラクテートに由来する無機成分]/[PAAの部分中和物]の重量比が0.9/99.1となるように混合液(U44)を調製した。具体的には、チタンラクテートのイソプロピルアルコール溶液(濃度10重量%)1.6重量部を、PAAの部分中和物の水溶液(濃度5重量%)100重量部に添加し、混合液(U44)を得た。
Al/Siのモル比が40.4/59.6、[TMOSおよびAIPに由来する無機成分]/[PAAの部分中和物]の重量比が40.3/59.7となるようにした以外は実施例3と同様の仕込み比で、混合液(U45)を調製した。具体的には、まず、TMOS50重量部をメタノール50重量部に溶解し、これに9.88重量%AIP水溶液(S45)461重量部を加えた。さらに、TMOSに対する水の割合が1.95モル当量となるよう蒸留水を3.3重量部と0.1Nの塩酸8.2重量部とを加え、10℃で5時間、加水分解および縮合反応を行い、混合液(T45)を得た。続いて、混合液(T45)を、蒸留水567重量部およびメタノール283重量部で希釈した後、攪拌しながらPAAの部分中和物水溶液(濃度13重量%)354重量部を速やかに添加し、固形分濃度5重量%の混合液(U45)を得た。
Al/Siのモル比が0.06/99.94、[TMOSおよびAIPに由来する無機成分]/[PAAの部分中和物]の重量比が70.0/30.0となるようにした以外は実施例3と同様の仕込み比で、混合液(U46)を調製した。具体的には、まず、TMOS50重量部をメタノール50重量部に溶解し、これに9.88重量%AIP水溶液(S46)0.4重量部を加えた。さらに、TMOSに対する水の割合が1.95モル当量となるよう蒸留水を3.3重量部と0.1Nの塩酸8.2重量部とを加え、10℃で5時間、加水分解および縮合反応を行い、混合液(T46)を得た。続いて、混合液(T46)を蒸留水243重量部、メタノール144重量部で希釈した後、攪拌しながらPAAの部分中和物水溶液(濃度13重量%)65重量部を速やかに添加し、固形分濃度5重量%の混合液(U46)を得た。
比較例6と同様の仕込み比で、反応時間のみを変えて、混合液(U47)を調製した。
比較例8では、実施例21で得られた混合液(U21)と同様の組成および方法で得た混合液(U48)を使用した。
Claims (17)
- 基材と、前記基材に積層された少なくとも1つのガスバリア性を有する層とを含むガスバリア性積層体であって、
前記ガスバリア性を有する層は、加水分解性を有する特性基を含有する少なくとも1種の化合物(L)の加水分解縮合物と、カルボキシル基およびカルボン酸無水物基から選ばれる少なくとも1つの官能基を含有する重合体(X)の中和物とを含む組成物からなり、
前記化合物(L)は、化合物(A)と、加水分解性を有する特性基が結合したSiを含有する化合物(B)とを含み、
前記化合物(A)は、以下の式(I)で表される少なくとも1種の化合物であり、
M1X1 mY1 n-m・・・(I)
[式(I)中、M1はAl、Ti、およびZrから選ばれるいずれか1つを表す。X1は、F、Cl、Br、I、OR1、R2COO、R3COCH2COR4、およびNO3から選ばれるいずれか1つを表す。Y1は、F、Cl、Br、I、OR5、R6COO、R7COCH2COR8、NO3およびR9から選ばれるいずれか1つを表す。R1、R2、R5およびR6は、それぞれ独立に、水素原子またはアルキル基を表す。R3、R4、R7、R8およびR9は、それぞれ独立にアルキル基を表す。nはM1の原子価と等しい。mは1~nの整数を表す。]
前記化合物(B)は、以下の式(II)で表される少なくとも1種の化合物を含み、
Si(OR10)pR11 4-p-qX2 q・・・(II)
[式(II)中、R10はアルキル基を表す。R11はアルキル基、アラルキル基、アリール基またはアルケニル基を表す。X2はハロゲン原子を表す。pおよびqは、それぞれ独立に0~4の整数を表す。1≦p+q≦4である。]
前記重合体(X)の前記官能基に含まれる-COO-基の少なくとも一部が2価以上の金属イオンで中和されており、
前記化合物(B)に占める前記式(II)で表される化合物の割合が80モル%以上であり、
前記組成物において、[前記化合物(A)に由来する前記M1原子のモル数]/[前記化合物(B)に由来するSi原子のモル数]の比が0.1/99.9~30.0/70.0の範囲にある、ガスバリア性積層体。 - 前記化合物(B)は、以下の式(III)で表される少なくとも1種の化合物をさらに含み、
Si(OR12)rX3 sZ3 4-r-s・・・(III)
[式(III)中、R12はアルキル基を表す。X3はハロゲン原子を表す。Z3は、カルボキシル基との反応性を有する官能基で置換されたアルキル基を表す。rおよびsは、それぞれ独立に0~3の整数を表す。1≦r+s≦3である。]
[前記式(II)で表される化合物に由来するSi原子のモル数]/[前記式(III)で表される化合物に由来するSi原子のモル数]の比が、99.5/0.5~80.0/20.0の範囲にある、請求項1に記載のガスバリア性積層体。 - 前記少なくとも1つのガスバリア性を有する層の厚さの合計が1μm以下であり、
20℃で85%RH雰囲気における酸素透過度が1.1cm3/(m2・day・atm)以下である、請求項1に記載のガスバリア性積層体。 - 前記M1がAlである、請求項1に記載のガスバリア性積層体。
- [前記化合物(L)に由来する無機成分の重量]/[前記化合物(L)に由来する有機成分の重量と前記重合体(X)に由来する有機成分の重量との合計]の比が、20.0/80.0~80.0/20.0の範囲にある、請求項1に記載のガスバリア性積層体。
- [前記化合物(L)に由来する無機成分の重量]/[前記化合物(L)に由来する有機成分の重量と前記重合体(X)に由来する有機成分の重量との合計]の比が、30.5/69.5~70.0/30.0の範囲にある、請求項1に記載のガスバリア性積層体。
- 前記重合体(X)が、ポリアクリル酸およびポリメタクリル酸から選ばれる少なくとも1種の重合体である、請求項1に記載のガスバリア性積層体。
- 前記重合体(X)の前記官能基に含まれる-COO-基の60モル%以上が前記金属イオンによって中和されている、請求項1に記載のガスバリア性積層体。
- 前記金属イオンが、カルシウムイオン、マグネシウムイオン、バリウムイオン、亜鉛イオン、鉄イオンおよびアルミニウムイオンからなる群より選ばれる少なくとも1つのイオンである、請求項1に記載のガスバリア性積層体。
- 前記ガスバリア性を有する層と水との接触角が20°以上である、請求項1に記載のガスバリア性積層体。
- 前記組成物が、前記化合物(L)および前記重合体(X)とは異なる化合物(P)を含み、
前記化合物(P)が2つ以上のアミノ基を含有する、請求項1に記載のガスバリア性積層体。 - 前記組成物が、前記化合物(L)および前記重合体(X)とは異なる化合物(Q)を含み、
前記化合物(Q)が2つ以上の水酸基を含有する、請求項1に記載のガスバリア性積層体。 - (i)加水分解性を有する特性基を含有する化合物(L)の加水分解縮合物と、重合体(X)とを含む組成物からなる層を基材上に形成する工程と、
(ii)2価以上の金属イオンを含む溶液に前記層を接触させる工程とを含み、
前記化合物(L)は、化合物(A)と、加水分解性を有する特性基が結合したSiを含有する化合物(B)とを含み、
前記化合物(A)は、以下の式(I)で表される少なくとも1種の化合物であり、
M1X1 mY1 n-m・・・(I)
[式(I)中、M1はAl、Ti、およびZrから選ばれるいずれか1つを表す。X1は、F、Cl、Br、I、OR1、R2COO、R3COCH2COR4、およびNO3から選ばれるいずれか1つを表す。Y1は、F、Cl、Br、I、OR5、R6COO、R7COCH2COR8、NO3およびR9から選ばれるいずれか1つを表す。R1、R2、R5およびR6は、それぞれ独立に、水素原子またはアルキル基を表す。R3、R4、R7、R8およびR9は、それぞれ独立にアルキル基を表す。nはM1の原子価と等しい。mは1~nの整数を表す。]
前記化合物(B)は、以下の式(II)で表される少なくとも1種の化合物を含み、
Si(OR10)pR11 4-p-qX2 q・・・(II)
[式(II)中、R10はアルキル基を表す。R11はアルキル基、アラルキル基、アリール基またはアルケニル基を表す。X2はハロゲン原子を表す。pおよびqは、それぞれ独立に0~4の整数を表す。1≦p+q≦4である。]
前記重合体(X)は、カルボキシル基およびカルボン酸無水物基から選ばれる少なくとも1つの官能基を含有する重合体であり、
前記化合物(B)に占める前記式(II)で表される化合物の割合が80モル%以上であり、
前記組成物において、[前記化合物(A)に由来する前記M1原子のモル数]/[前記化合物(B)に由来するSi原子のモル数]の比が0.1/99.9~30.0/70.0の範囲にある、ガスバリア性積層体の製造方法。 - 前記(i)の工程が、
(i-a)前記化合物(A)および前記化合物(A)の部分加水分解縮合物から選ばれる少なくとも1種の化合物と、カルボキシル基を含有し分子量が100以下である化合物(D)と、を含む溶液(S)を調製する工程と、
(i-b)前記化合物(B)および前記化合物(B)の部分加水分解縮合物から選ばれる少なくとも1種の化合物と前記溶液(S)とを混合することによって溶液(T)を調製する工程と、
(i-c)前記溶液(T)中において、前記化合物(A)と前記化合物(B)とを含む複数の化合物の加水分解縮合物を形成する工程と、
(i-d)前記(i-c)の工程を経た前記溶液(T)と前記重合体(X)とを混合することによって溶液(U)を調製する工程と、
(i-e)前記溶液(U)を前記基材に塗工して乾燥させることによって前記層を形成する工程と、を含む請求項13に記載の製造方法。 - 前記化合物(B)は、以下の式(III)で表される少なくとも1種の化合物をさらに含み、
Si(OR12)rX3 sZ3 4-r-s・・・(III)
[式(III)中、R12はアルキル基を表す。X3はハロゲン原子を表す。Z3は、カルボキシル基との反応性を有する官能基で置換されたアルキル基を表す。rおよびsは、それぞれ独立に0~3の整数を表す。1≦r+s≦3である。]
[前記式(II)で表される化合物に由来するSi原子のモル数]/[前記式(III)で表される化合物に由来するSi原子のモル数]の比が、99.5/0.5~80.0/20.0の範囲にある、請求項13に記載の製造方法。 - 前記(ii)の工程において、前記重合体(X)の前記官能基に含まれる-COO-基の60モル%以上を前記金属イオンで中和する、請求項13に記載の製造方法。
- 前記(i)の工程ののちであって前記(ii)の工程の前および/または後に、前記層を120℃~240℃の温度で熱処理する工程をさらに含む、請求項13に記載の製造方法。
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WO2013051286A1 (ja) | 2011-10-05 | 2013-04-11 | 株式会社クラレ | 複合構造体、それを用いた包装材料および成形品、ならびに、それらの製造方法およびコーティング液 |
WO2013051287A1 (ja) * | 2011-10-05 | 2013-04-11 | 株式会社クラレ | 複合構造体およびそれを用いた製品、ならびに複合構造体の製造方法 |
KR20140079813A (ko) | 2011-10-05 | 2014-06-27 | 가부시키가이샤 구라레 | 복합 구조체, 이를 사용한 포장 재료 및 성형품, 및 이들의 제조 방법 및 코팅액 |
CN103958185A (zh) * | 2011-10-05 | 2014-07-30 | 株式会社可乐丽 | 复合结构体和使用其的产品、以及复合结构体的制造方法 |
JPWO2013051286A1 (ja) * | 2011-10-05 | 2015-03-30 | 株式会社クラレ | 複合構造体、それを用いた包装材料および成形品、ならびに、それらの製造方法およびコーティング液 |
JPWO2013051287A1 (ja) * | 2011-10-05 | 2015-03-30 | 株式会社クラレ | 複合構造体およびそれを用いた製品、ならびに複合構造体の製造方法 |
US9403998B2 (en) | 2011-10-05 | 2016-08-02 | Kuraray Co., Ltd. | Composite structure, product using same, and method for producing composite structure |
US9840630B2 (en) | 2011-10-05 | 2017-12-12 | Kuraray Co., Ltd. | Composite structure, packaging material and formed product using same, production methods thereof, and coating liquid |
Also Published As
Publication number | Publication date |
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ES2466022T3 (es) | 2014-06-09 |
JP4463876B2 (ja) | 2010-05-19 |
EP2266794A4 (en) | 2012-12-12 |
EP2266794A1 (en) | 2010-12-29 |
KR20100134097A (ko) | 2010-12-22 |
KR101159060B1 (ko) | 2012-07-03 |
AU2009234738A1 (en) | 2009-10-15 |
EP2266794B1 (en) | 2014-05-07 |
US20110027580A1 (en) | 2011-02-03 |
AU2009234738B2 (en) | 2012-01-19 |
CN101990495A (zh) | 2011-03-23 |
JPWO2009125800A1 (ja) | 2011-08-04 |
US8617703B2 (en) | 2013-12-31 |
CN101990495B (zh) | 2013-09-18 |
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