WO2009125801A1 - 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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- WO2009125801A1 WO2009125801A1 PCT/JP2009/057226 JP2009057226W WO2009125801A1 WO 2009125801 A1 WO2009125801 A1 WO 2009125801A1 JP 2009057226 W JP2009057226 W JP 2009057226W WO 2009125801 A1 WO2009125801 A1 WO 2009125801A1
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- gas barrier
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- laminate
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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.
- 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 display a high oxygen barrier property even if the gas barrier layer is thin, maintain a high oxygen barrier property even when retorting is performed under severe conditions, and further, printing,
- An object of the present invention is to provide a gas barrier laminate having excellent dimensional stability at the time of processing such as laminating and flexibility of the gas barrier laminate, and further having mechanical properties close to those inherent in the base film.
- 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 base material and at least one gas barrier property layer laminated on the base material.
- the compound (L) includes at least one compound (A) containing a metal atom to which a hydrolyzable characteristic group is bonded, and is included in the functional group of the polymer (X).
- At least a part of the —COO— group is neutralized and / or reacted with the compound (P) containing two or more amino groups, and contained in the functional group of the polymer (X).
- at least a part of the —COO— group is neutralized with a metal ion having a valence of 2 or more; [equivalent of amino group contained in the compound (P)] / [of the polymer (X)
- the equivalent ratio of —COO— groups contained in the functional group] is in the range of 0.2 / 100 to 20.0 / 100.
- the method of the present invention for producing a gas barrier laminate has hydrolyzability with (i) a polymer (X) containing at least one functional group selected from a carboxyl group and a carboxylic anhydride group.
- the compound (L) includes at least one compound (A) containing a metal atom to which a hydrolyzable characteristic group is bonded, and in the composition, the polymer (L) In the composition, at least a part of —COO— group contained in the functional group of X) is neutralized and / or reacted with the compound (P) containing two or more amino groups, Compound( ) Equivalents of amino groups contained in] / [the ratio of equivalents] of -COO- group contained in the functional group of the polymer (X) is in the range of 0.2 / 100 to 20.0 / 100.
- Si may be classified into a semimetal, in this specification, it describes as one of metals.
- 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 composed of a composition containing the hydrolysis condensate of compound (L) and polymer (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 polymer (X) is a polymer containing at least one functional group selected from a carboxyl group and a carboxylic anhydride group.
- 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) of the polymer (X) is neutralized and / or reacted with the compound (P) containing two or more amino groups.
- at least a part of the —COO— group contained in the functional group (F) is neutralized with a divalent or higher metal ion.
- at least a part of the functional group constitutes a salt with a divalent or higher valent metal ion.
- the ratio of [equivalent of amino group contained in compound (P)] / [equivalent of -COO-group contained in functional group of polymer (X)] was 0.2 / 100 to 20. It is in the range of 0/100.
- [equivalent of amino group contained in compound (P)] / [equivalent of -COO- group contained in functional group of polymer (X)] is "number of moles of amino group contained in compound (P)" ] / [Number of moles of —COO— group contained in the functional group of the polymer (X)].
- 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 the compound (L) and the polymer (X) in the composition is, for example, 50% or more, 70% or more, 80% or more, 90% or more, 95% 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.
- the hydrolyzate condenses to form a compound in which metal atoms are bonded through oxygen. When this condensation is repeated, it becomes a compound that can be regarded as a metal oxide substantially.
- the compound (L) contains a hydrolyzable characteristic group (functional group), and these groups are not bonded.
- Hydrolysis and condensation reactions do not occur or are very slow. Therefore, in that case, it is difficult to obtain the effect 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.
- Examples of the characteristic group having hydrolyzability include groups exemplified as OR 1 and X 1 in the following formula (I).
- the compound (L) includes at least one compound (A) including a metal atom to which a hydrolyzable characteristic group is bonded.
- a typical compound (A) is at least one compound represented by the following formula (I).
- M 1 (OR 1 ) q R 2 pqr X 1 r (I) [In Formula (I), M 1 represents Si, Al, Ti, Zr, Cu, Ca, Sr, Ba, Zn, Ga, Y, Ge, Pb, Sb, V, Ta, W, La, or Nd.
- R 1 represents an alkyl group.
- R 2 represents an alkyl group, an aralkyl group, an aryl group or an alkenyl group.
- X 1 represents a halogen atom.
- p is equal to the valence of M 1 .
- q represents an integer of 0 to p.
- r represents an integer of 0 to p. 1 ⁇ q + r ⁇ p. ]
- M 1 represents an atom selected from Si, Al, Ti, Zr, Cu, Ca, Sr, Ba, Zn, Ga, Y, Ge, Pb, Sb, V, Ta, W, La, and Nd.
- Si, Al, Ti or Zr is preferable, and Si, Al or Ti is particularly preferable.
- the alkyl group represented by R 1 include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a t-butyl group, and the like, and preferably a methyl group or an ethyl group. is there.
- 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 2 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 include benzyl group, phenethyl group, and trityl group.
- examples of the aryl group represented by R 2 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 represented by the formula (I) include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, octyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane.
- Silane alkoxides such as ethoxysilane, chlorotrimethoxysilane, chlorotriethoxysilane, dichlorodimethoxysilane, dichlorodiethoxysilane, trichloromethoxysilane, and trichloroethoxysilane; halogenated silanes such as vinyltrichlorosilane, tetrachlorosilane, and tetrabromosilane; Alkoxy titanium compounds such as titanium tetramethoxide, titanium tetraethoxide, titanium tetraisopropoxide, titanium methyltriisopropoxide; tetrachlorotitanium, etc.
- Titanium rogenide alkoxy aluminum compounds such as aluminum trimethoxide, aluminum triethoxide, aluminum triisopropoxide, aluminum methyl diisopropoxide, aluminum tributoxide, diethoxyaluminum chloride; zirconium tetraethoxide, zirconium tetraisopropoxy And alkoxyzirconium compounds such as zirconium methyltriisopropoxide.
- Preferred examples of the compound (A) represented by the formula (I) include tetramethoxysilane and tetraethoxysilane.
- Compound (L) comprises at least one compound (B) containing a metal atom in which a hydrolyzable characteristic group and an alkyl group substituted with a functional group having reactivity with a carboxyl group are bonded. May be included.
- a typical compound (B) is at least one compound represented by the following formula (II).
- M 2 (OR 3 ) n X 2 k Z 2 mnk (II)
- M 2 represents Si, Al, Ti, Zr, Cu, Ca, Sr, Ba, Zn, Ga, Y, Ge, Pb, Sb, V, Ta, W, La, or Nd.
- R 3 represents an alkyl group.
- X 2 represents a halogen atom.
- Z 2 represents an alkyl group substituted with a functional group having reactivity with a carboxyl group.
- m is equal to the valence of M 2 .
- n represents an integer of 0 to (m ⁇ 1).
- k represents an integer of 0 to (m ⁇ 1). 1 ⁇ n + k ⁇ (m ⁇ 1). ]
- M 2 is selected from Si, Al, Ti, Zr, Cu, Ca, Sr, Ba, Zn, Ga, Y, Ge, Pb, Sb, V, Ta, W, La and Nd. Represents an atom. M 2 is preferably Si, Al, Ti or Zr, and particularly preferably Si.
- the alkyl group represented by R 3 include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, and a t-butyl group, preferably a methyl group or an ethyl group. is there.
- 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 functional group having reactivity with a carboxyl group that Z 2 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, or a carbodiimide group.
- An epoxy group, an amino group, an isocyanate group, a ureido group or a halogen atom is preferred, and for example, at least one selected from an epoxy group, an amino group and an isocyanate group is more preferred.
- Examples of the alkyl group substituted with such a functional group include those exemplified for R 3 .
- Specific examples of the compound represented by the formula (II) include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropyltrichlorosilane, ⁇ -aminopropyltrimethoxysilane.
- Preferred examples of the compound represented by the formula (II) include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -chloropropyltrimethoxysilane, ⁇ -chloropropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane and ⁇ -aminopropyltriethoxysilane.
- the ratio of [number of moles of M 1 atom derived from the compound represented by formula (I)] / [number of moles of M 2 atom derived from the compound represented by formula (II)] was 99.5 / 0. It is preferably in the range of 5 to 80.0 / 20.0. When this ratio is larger than 99.5 / 0.5, the hot water resistance of the gas barrier laminate may be lowered. Moreover, when this ratio becomes smaller than 80.0 / 20.0, the gas barrier property of the gas barrier laminate may be deteriorated. This ratio is more preferably in the range of 98.0 / 2.0 to 89.9 / 10.1.
- [the number of moles of M 1 atom derived from the compound represented by formula (I)] is substantially the same as the [number of moles of the compound represented by formula (I)] used for generating the hydrolysis condensate.
- [the number of moles of M 2 atom derived from the compound represented by the formula (II)] is substantially equal to the [number of moles of the compound represented by the formula (II)] used for the production of the hydrolysis condensate. be equivalent to. Therefore, in the following description, the ratio may be replaced with [number of moles of compound represented by formula (I)] / [number of moles of compound represented by formula (II)].
- Ratio of the compound represented by formula (I) and the compound represented by formula (II) in the compound (L) in the case where the compound represented by formula (II) is not included, in the formula (I)
- the proportion of the compound represented is, for example, 80 mol% or more, 90 mol% or more, 95 mol% or more, 95 mol% or more, 98 mol% or more, 99 mol% or more, or 100 mol%.
- the number of molecules condensed in the hydrolysis condensate of the compound (L) can be controlled by the amount of water, the type and concentration of the catalyst used at the time of hydrolysis / condensation, the temperature at which the hydrolysis condensation is performed, and the like.
- the sum of 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. More preferably, it is in the range of ⁇ 69.9 / 30.1.
- 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 A compound represented by M 1 O p / 2 is obtained. Further, when the compound (A) represented by the formula (I) contains R 2 , when it is completely hydrolyzed and condensed, the composition formula is M 1 O (q + r) / 2 R 2 (pqr ) . Of this compound, the portion of M 1 O (q + r) / 2 is a metal oxide.
- R 2 is an organic component derived from the compound (L). Moreover, it calculates similarly about a compound (B). At this time, Z 2 is an organic component derived from the compound (L).
- the weight of the ions is also the weight of the organic component derived from the polymer (X). Added to.
- the compound (P) containing two or more amino groups is a compound different from the compound (L) and the polymer (X).
- Specific examples of the compound (P) include alkylene diamines, polyalkylene polyamines, alicyclic polyamines, aromatic polyamines, polyvinylamines, etc., and the gas barrier property of the gas barrier laminate is better. From the viewpoint of, 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.
- the compound (P) is preferably at least one selected from the group consisting of ethylenediamine, propylenediamine, and chitosan, for example, from the viewpoint that the gas barrier properties of the gas barrier laminate are improved. .
- the ratio of [equivalent of amino group contained in compound (P)] / [equivalent of -COO-group contained in functional group of polymer (X)] was 0.2 / It is in the range of 100 to 20.0 / 100 (for example, the range of 0.2 / 100 to 19.4 / 100). In this range, the gas barrier laminate exhibits good gas barrier properties. When the ratio is smaller than 0.2 / 100, the hot water resistance of the gas barrier laminate is lowered, and the gas barrier property after retorting is lowered. On the other hand, when the ratio is larger than 20.0 / 100, the gas barrier properties before and after the retort treatment of the gas barrier laminate are deteriorated.
- the above ratio is preferably in the range of 1.0 / 100 to 4.9 / 100 for the reasons described above.
- the composition constituting the gas barrier layer of the present invention may contain a compound (Q) containing two or more hydroxyl groups. According to this configuration, the gas barrier property after elongation of the gas barrier laminate is improved. More specifically, by adding the compound (Q), even if the gas barrier laminate is stretched, the gas barrier layer is less likely to be damaged, and as a result, the gas barrier layer retains high gas barrier properties even after being stretched. The gas barrier property of the gas barrier laminate is hardly lowered even in a state after elongation due to tension at the time of processing such as 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.
- Carboxylic acid-containing polymer (polymer (X)) 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 (polymer (X)) may be referred to as a “carboxylic acid-containing polymer”.
- the neutralized product of the carboxylic acid-containing polymer can be obtained by neutralizing at least a 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. Specifically, 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.
- carboxylic acid-containing units (G) 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 polymer is neutralized with, for example, 10 mol% or more (for example, 15 mol% or more) with a divalent or higher metal ion.
- the carboxyl group and / or carboxylic anhydride group in the carboxylic acid-containing polymer is neutralized with a divalent or higher metal ion, 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.
- 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 resins such as nylon 12; polystyrene, poly (meth) acrylate, polyacrylonitrile, polyvinyl acetate, polycarbonate, polyarylate, regenerated cellulose, polyimide, polyetherimide, polysulfone, polyethersulfone, polyetheretherketone And a film obtained by molding an ionomer resin or 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, but because the processing suitability of the gas barrier laminate of the present invention is excellent, such as a stretched film, A biaxially stretched film is particularly preferable.
- 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 laminate of the present invention may further include an adhesive layer (H) disposed between the base material and the gas barrier layer.
- the 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. I found it.
- an adhesive resin 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 can be 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 a layer made of a composition containing the polymer (X) and the hydrolysis condensate of the compound (L) on the substrate.
- the layer is formed directly on the substrate or is formed on the substrate via another layer.
- at least a part of —COO— group contained in the functional group (F) of the polymer (X) is neutralized and / or reacted with the compound (P) containing two or more amino groups.
- the ratio of [equivalent of amino group contained in compound (P)] / [equivalent of —COO— group contained in functional group (F) of polymer (X)] was 0.2 / 100. It is in the range of ⁇ 20.0 / 100.
- the compounds contained in the compound (L) and the ratio of these compounds are the same as those described for the composition constituting the gas barrier layer.
- 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) since mixing of a compound (P) and a carboxylic acid containing polymer may cause both to react and the coating of a solution (U) may become difficult, a process (i) is compound (P) and It is preferable to include the step (ia) of preparing the solution (S) containing the acid (R).
- the method for adjusting the solution (U) is not particularly limited as long as the solution (U) can be applied, and examples thereof include the following methods.
- a method in which the compound (L), the solution (S) and, if necessary, a solvent are added to and mixed with the solution in which the polymer (X) is dissolved can be employed.
- an oligomer (V) (one kind of hydrolysis condensate) is prepared from the compound (L) in the presence or absence of a solvent, and the polymer (X) is dissolved in the oligomer (V).
- a method of mixing the prepared solution and the solution (S) can also be employed.
- a compound (L) and an oligomer (V) may be added to a solution independently, and may be added to a solvent with the form of the solution which dissolved them.
- a gas barrier laminate having particularly excellent gas barrier properties can be obtained by using the method (2).
- the method (2) will be described more specifically.
- the step (i) includes (ia) a step of preparing a solution (S) containing the compound (P) and the acid (R), and (ib) the compound (L). Preparing a solution (T) containing an oligomer obtained by hydrolyzing and condensing the solution, and (ic) a solution (U) containing the solution (S), the solution (T) and the polymer (X). A step of preparing, and (id) a step of forming the layer by applying the solution (U) to a substrate and drying it. Either step (ia) or step (ib) may be performed first or simultaneously.
- step (ia) a solution (S) containing compound (P) and acid (R) is prepared.
- S acid
- R acid
- the acid (R) produced by the exchange reaction between the salt of the amino group of compound (P) and acid (R) and the —COO— group of the carboxylic acid polymer is used in the drying step of step (id). It is preferably removed from the gas barrier layer.
- the acid (R) is not particularly limited, but examples of preferable acid (R) include hydrochloric acid, nitric acid, carbonic acid, and acetic acid from the viewpoint of easy removal from the gas barrier layer in the drying step (id). Of these, hydrochloric acid is preferred.
- the amount of acid (R) used in solution (S) is such that the ratio of [equivalent of acid (R)] / [equivalent of amino group of compound (P)] is 0.5 / 1 or more. Good. If the conditions of 0.5 / 1 or more are satisfied, gelation at the time of mixing with the carboxylic acid-containing polymer can be prevented.
- the ratio of [equivalent of acid (R)] / [equivalent of amino group of compound (P)] is in the range of 0.5 / 1 to 10/1. It is preferably in the range of 0.7 / 1 to 5/1, more preferably in the range of 0.7 / 1 to 2/1.
- oligomer (V) by hydrolyzing and condensing compound (L) in a reaction system containing compound (L), an acid catalyst, water, and if necessary, an organic solvent.
- a technique used in a known sol-gel method can be applied.
- the compound (L) may be previously hydrolyzed and condensed.
- compound (L) compound (L), compound (L) partially hydrolyzed, compound (L) completely hydrolyzed, compound (L) partially hydrolyzed and condensed, and compound (L ) May be referred to as “compound (L) -based component”.
- a known acid can be used as the acid catalyst used in the step (ib).
- hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, benzoic acid, acetic acid, lactic acid, butyric acid, carbonic acid, oxalic acid, malein An acid etc. are mentioned.
- hydrochloric acid, sulfuric acid, nitric acid, acetic acid, lactic acid, and butyric acid are particularly preferable.
- 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 the step (ib) varies depending on the type of the compound (L), but is 0.05 to 10 equivalents relative to 1 equivalent of the hydrolyzable characteristic group of the compound (L). Preferably, it is in the range of 0.1 to 5 equivalents, more preferably in the range of 0.2 to 3 equivalents. When the amount of water used is in this range, a gas barrier laminate having particularly excellent gas barrier properties can be obtained.
- step (ib) when a component containing water such as hydrochloric acid is used, it is preferable to determine the amount of water used in consideration of the amount of water introduced by the component.
- 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 used is not particularly limited, but the amount is preferably 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. preferable.
- the temperature of the reaction system is not necessarily limited, but is usually in the range of 2 to 100 ° C., preferably 4 to It is in the range of 60 ° C., 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 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 0.1 The range is up to 6 hours.
- the reaction can be performed in an atmosphere of various gases such as air, carbon dioxide, nitrogen, and argon.
- step (ib) the entire amount of compound (L) may be added to the reaction system at once, or may be added to the reaction system in small portions several times. In any case, it is preferable that the total amount of the compound (L) used satisfies the above preferable range.
- Step (ic) includes a solution (T) containing the oligomer (V) obtained in step (ib), a solution (S) prepared in step (ia), and a polymer (X).
- the method of mixing (2) the solution (S) with the solution in which the carboxylic acid-containing polymer is dissolved, and adding the solution to the solution (T) and mixing can also be employed. Furthermore, (3) a method in which a solution in which a carboxylic acid-containing polymer is dissolved is added to and mixed with the solution (T), and then the solution (S) is added and mixed.
- the solution (T) to be added the solution in which the carboxylic acid-containing polymer is dissolved, and the solution (S) may be added at once. , May be added in portions.
- a solution in which the carboxylic acid-containing polymer is dissolved in step (ic) 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; methyl cellosolve; Glycol derivatives such as ethyl cellosolve and n-butyl cellosolve; glycerin; acetonitrile, dimethylformamide, dimethyl sulfoxide, sulfolane, dimethoxyethane and the like can also 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 gas barrier laminate, preferably 0.7 to 3 More preferably, it is in the range of 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, and preferably 1.0 to 6. A range of 0 is more preferable, and a range of 1.5 to 4.0 is even more preferable.
- the pH of the solution (U) can be adjusted by a known method.
- 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
- basic compounds such as sodium carbonate and sodium acetate.
- 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. it can.
- Step (id) will be described.
- the state of the solution (U) prepared in the step (ic) changes with time, and finally becomes a gel-like 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 (ic) is applied to at least one surface of the substrate in the step (id).
- 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 contact angle of water with respect to the gas barrier layer surface is measured and the contact angle is smaller than the above-mentioned predetermined range, by increasing the reaction time of the step (ib) and the step (ic), 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 step (ib) and the step (ic).
- the laminate (I) obtained by the above step is brought into contact with a solution containing metal ions having a valence of 2 or more (hereinafter sometimes referred to as solution (IW)) (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 base material 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 laminated body (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. By performing the heat treatment, the amidation reaction of the amino group of the compound (P) and the —COO— group of the carboxylic acid-containing polymer further proceeds.
- the oxygen barrier properties and appearance (transparency, etc.) after boil treatment and retort treatment are superior, and the gas barrier properties exhibit good oxygen barrier properties and appearance (transparency, etc.) even after retorting under severe retort conditions.
- a laminate is obtained.
- 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.
- the surface of the base material is treated (treatment with an anchor coating agent or application of an adhesive) before application of the solution (U). You may give it.
- 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 (8).
- description of the abbreviation used by the following description about a measuring method and an evaluation method may be mentioned later.
- 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 the same oxygen barrier property before and after the retort treatment as the laminated body of Reference Examples 1 and 2 although the coat layer is thin. Or more, and 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.
- EDA ethylenediamine
- the ratio of [weight of inorganic component derived from tetramethoxysilane (TMOS)] / [weight of partially neutralized PAA] was 30.0 / 70.0, and [amino group of EDA] / [PAA
- the mixed solution (U1) was prepared so that the equivalent ratio of [carboxyl group] was 0.2 / 100. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol. Subsequently, 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 was performed at 10 ° C. for 1 hour.
- 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 material having an anchor coat layer (AC / PET) was prepared.
- PET polyethylene terephthalate film
- 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 wt% aqueous calcium acetate 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.
- the gas barrier layer was colorless and transparent and had a very good appearance.
- the degree of ionization, the oxygen permeability before retorting, the contact angle, the tensile strength and elongation, the Young's modulus, and the dry heat shrinkage rate were measured by the methods described above.
- Example 2 A partially neutralized aqueous solution of PAA and an EDA hydrochloride aqueous solution were prepared in the same manner as in Example 1. And the liquid mixture (U2) was prepared by the same preparation ratio as Example 1 except having made the equivalent ratio of [amino group of EDA] / [carboxyl group of PAA] 1.0 / 100. Specifically, first, the mixture (T2) prepared by the same composition and method as the mixture (T1) of Example 1 was diluted with 567 parts by weight of distilled water and 283 parts by weight of methanol, and then stirred with PAA.
- 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 the laminate was performed in the same manner as in Example 1.
- Example 3 to 6 and 33 the amount of EDA added was changed. From these examples, the ratio of [equivalent of amino group contained in compound (P)] / [equivalent of -COO-group contained in functional group of polymer (X)] was 0.2 / 100 to 20. When in the range of 0/100, it was confirmed that excellent gas barrier properties and hot water resistance were exhibited. When the compound (P) is less than this range, the hot water resistance is lowered, and when it is more, the gas barrier property is lowered (see Comparative Examples 3 and 4). Further, from the viewpoint of better gas barrier properties and hot water resistance, the ratio is preferably in the range of 1.0 / 100 to 4.9 / 100 (see Examples 5 and 6).
- Example 3 A partially neutralized aqueous solution of PAA and an EDA hydrochloride aqueous solution were prepared in the same manner as in Example 1. And the liquid mixture (U3) was prepared by changing only reaction time by the preparation ratio similar to Example 1.
- FIG. 3 A partially neutralized aqueous solution of PAA and an EDA hydrochloride aqueous solution were prepared in the same manner as in Example 1.
- the liquid mixture (U3) was prepared by changing only reaction time by the preparation ratio similar to Example 1.
- TMOS TMOS dissolved in 50 parts by weight of methanol. Thereto was added 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid so that the ratio of water to TMOS was 1.95 molar equivalents, and hydrolysis and condensation reaction at 10 ° C. for 5 hours. And a liquid mixture (T3) was obtained. Next, after the mixed liquid (T3) was diluted with 567 parts by weight of distilled water and 283 parts by weight of methanol, 354 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight) was rapidly added while stirring. Further, 1.27 parts by weight of an EDA hydrochloride aqueous solution (S3) was added to obtain a mixed liquid (U3) having a solid content concentration of 5% by weight.
- Example 3 Using the mixed solution (U3), coating, heat treatment, ionization and drying were performed in the same manner as in Example 1 to obtain a laminate (A3). Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (3). Evaluation of the laminate and laminate was performed in the same manner as in Example 1.
- Example 4 A partially neutralized aqueous solution of PAA and an EDA hydrochloride aqueous solution were prepared in the same manner as in Example 1. And the liquid mixture (U4) was prepared by the preparation ratio similar to Example 3 except having made the equivalent ratio of [amino group of EDA] / [carboxyl group of PAA] 19.4 / 100. Specifically, first, the mixture (T4) prepared by the same composition and method as the mixture (T3) of Example 3 was diluted with 567 parts by weight of distilled water and 283 parts by weight of methanol, and then stirred.
- 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 the laminate was performed in the same manner as in Example 1.
- Example 5 A partially neutralized aqueous solution of PAA and an EDA hydrochloride aqueous solution were prepared in the same manner as in Example 1. And the liquid mixture (U5) was prepared by the preparation ratio similar to Example 3 except having made the equivalent ratio of [amino group of EDA] / [carboxyl group of PAA] 4.9 / 100. Specifically, first, the mixture (T5) prepared by the same composition and method as the mixture (T3) of Example 3 was diluted with 567 parts by weight of distilled water and 283 parts by weight of methanol, and then stirred.
- 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 the laminate was performed in the same manner as in Example 1.
- Example 6 A partially neutralized aqueous solution of PAA and an EDA hydrochloride aqueous solution were prepared in the same manner as in Example 1. And the liquid mixture (U6) was prepared by the preparation ratio similar to Example 3 except having made the equivalent ratio of [amino group of EDA] / [carboxyl group of PAA] become 1.0 / 100. Specifically, first, the liquid mixture (T6) prepared by the same composition and method as the liquid mixture (T3) of Example 3 was diluted with 567 parts by weight of distilled water and 283 parts by weight of methanol, and then stirred with PAA.
- 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 EDA hydrochloride aqueous solution were prepared in the same manner as in Example 1. Subsequently, the molar ratio of [TMOS] / [ ⁇ -glycidoxydoxypropyltrimethoxysilane (GPTMOS)] is 99.5 / 0.5, [inorganic component derived from TMOS and GPTMOS] / [organic component of GPTMOS) And a partially neutralized product of PAA] in a mixed solution (so that the molar ratio of 30.0 / 70.0 and [amino group of EDA] / [carboxyl group of PAA] is 1.0 / 100) U7) was prepared.
- TMOS and GPTMOS were dissolved in 50 parts by weight of methanol. Thereto was added 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid so that the ratio of water to the total of TMOS and GPTMOS was 1.95 molar equivalents, and 5 hours at 10 ° C. Hydrolysis and condensation reaction were performed to obtain a mixed solution (T7). Subsequently, after the mixed solution (T7) was diluted with 566 parts by weight of distilled water and 284 parts by weight of methanol, 352 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight) was rapidly added while stirring. Further, 6.3 parts by weight of an EDA hydrochloride aqueous solution (S7) was added to obtain a mixed solution (U7) having a solid content concentration of 5% by weight.
- 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 the laminate was performed in the same manner as in Example 1.
- Example 8 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 the laminate was performed in the same manner as in Example 1.
- Example 9 A mixed solution (U9) was prepared with the same charging ratio as in Example 7 except that the molar ratio of TMOS / GPTMOS was 89.9 / 10.1. Specifically, first, 42.6 parts by weight of TMOS and 7.4 parts by weight of GPTMOS were dissolved in 50 parts by weight of methanol. Thereto was added 3.2 parts by weight of distilled water and 7.8 parts by weight of 0.1N hydrochloric acid 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
- 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 the laminate was performed in the same manner as in Example 1.
- Example 10 A partially neutralized aqueous solution of PAA and an EDA hydrochloride aqueous solution were prepared in the same manner as in Example 1. Subsequently, the molar ratio of [TMOS] / [GPTMOS] was 98.0 / 2.0, and the weight ratio of [inorganic component derived from TMOS and GPTMOS] / [partial neutralized product of organic component of GPTMOS and PAA]. Was 32.4 / 67.6, and a mixed solution (U10) was prepared so that the molar ratio of [amino group of EDA] / [carboxyl group of PAA] was 1.1 / 100.
- TMOS and GPTMOS were dissolved in 50 parts by weight of methanol. Thereto was added 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid so that the ratio of water to the total of TMOS and GPTMOS was 1.95 molar equivalents, and the mixture was hydrolyzed at 10 ° C. for 5 hours. Decomposition
- disassembly and condensation reaction were performed and the liquid mixture (T10) was obtained.
- 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 the laminate was performed in the same manner as in Example 1. Furthermore, the oxygen permeability after 10% elongation was also measured.
- Example 11 A mixed solution (U11) was obtained with the same charging ratio as in Example 7 except that the molar ratio of TMOS to 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. Thereto was added 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid so that the ratio of water to the total of TMOS and GPTMOS was 1.95 molar equivalents, and the mixture was hydrolyzed at 10 ° C. for 5 hours. Decomposition
- 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 the laminate was performed in the same manner as in Example 1.
- Example 12 A mixed liquid (U12) was prepared at the same charging ratio as in Example 7 except that the molar ratio of TMOS / GPTMOS was 70.0 / 30.0. Specifically, first, 30 parts by weight of TMOS and 20 parts by weight of GPTMOS were dissolved in 50 parts by weight of methanol. Thereto was added 2.9 parts by weight of distilled water and 7.0 parts by weight of 0.1N hydrochloric acid so that the ratio of water to the total of TMOS and GPTMOS was 1.95 molar equivalents, Decomposition
- 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 the laminate was performed in the same manner as in Example 1.
- Example 13 A partially neutralized aqueous solution of PAA and an EDA hydrochloride aqueous solution were prepared in the same manner as in Example 1. The same as in Example 10 except that the weight ratio of [inorganic component derived from TMOS and GPTMOS] / [partial neutralized product of organic component of GPTMOS and PAA] was 20.0 / 80.0.
- a mixed solution (U13) was prepared at a charging ratio. Specifically, first, a mixed solution (T13) was obtained by the same composition and method as the mixed solution (T10) of Example 10.
- 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 the laminate was performed in the same manner as in Example 1.
- Example 14 A partially neutralized aqueous solution of PAA and an EDA hydrochloride aqueous solution were prepared in the same manner as in Example 1. The same as in Example 10 except that the weight ratio of [inorganic component derived from TMOS and GPTMOS] / [partial neutralized product of organic component of GPTMOS and PAA] was 80.0 / 20.0.
- a mixed solution (U14) was prepared at a charging ratio. Specifically, first, a mixed solution (T14) was obtained by the same composition and method as the mixed solution (T10) of Example 10.
- 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 the laminate was performed in the same manner as in Example 1.
- Example 15 A partially neutralized aqueous solution of PAA and an EDA hydrochloride aqueous solution were prepared in the same manner as in Example 1. The same as in Example 10 except that the weight ratio of [inorganic component derived from TMOS and GPTMOS] / [partial neutralized product of organic component of GPTMOS and PAA] was 69.9 / 30.1. A mixed liquid (U15) was obtained at a charging ratio. Specifically, first, a mixed solution (T15) was obtained by the same composition and method as the mixed solution (T10) of Example 10.
- 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 the laminate was performed in the same manner as in Example 1.
- Example 16 A partially neutralized aqueous solution of PAA and an EDA hydrochloride aqueous solution were prepared in the same manner as in Example 1. The same as in Example 10 except that the weight ratio of [inorganic component derived from TMOS and GPTMOS] / [partial neutralized product of organic component of GPTMOS and PAA] was 10.0 / 90.0.
- a mixed liquid (U16) was obtained at a charging ratio. Specifically, first, a mixed solution (T16) was obtained by the same composition and method as the mixed solution (T10) of Example 10.
- 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 the laminate was performed in the same manner as in Example 1.
- Example 17 A partially neutralized aqueous solution of PAA and an EDA hydrochloride aqueous solution were prepared in the same manner as in Example 1. The same as in Example 10 except that the weight ratio of [inorganic component derived from TMOS and GPTMOS] / [partial neutralized product of organic component of GPTMOS and PAA] was 90.0 / 10.0.
- a mixed liquid (U17) was obtained at a charging ratio. Specifically, first, a mixed solution (T17) was obtained by the same composition and method as the mixed solution (T10) of Example 10.
- 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 the laminate was performed in the same manner as in Example 1.
- Examples 10 and 18 to 20 the type of compound (P) was changed. From these examples, it was confirmed that ethylenediamine, propylenediamine, and chitosan were preferable as the compound (P).
- Example 18 1N-HCl was added to PDA so that the equivalent ratio of [amino group contained in propylenediamine (PDA)] / [HCl] was 1/1 to obtain PDA hydrochloride aqueous solution (S18).
- a mixed solution (U18) was obtained by the same composition and method as the mixed solution (U10) of Example 10 except that the EDA hydrochloride aqueous solution was changed to the PDA hydrochloride aqueous solution (S18).
- Example 10 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 10.
- Example 19 1N-HCl was added to chitosan so that the equivalent ratio of [amino group contained in chitosan] / [HCl] was 1/1 to obtain an aqueous chitosan hydrochloride solution (S19).
- a mixed solution (U19) was obtained by the same composition and method as the mixed solution (U10) of Example 10 except that the EDA hydrochloride aqueous solution was changed to a chitosan hydrochloride aqueous solution (S19).
- Example 1 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 1.
- Example 20 1N-HCl was added to HMDA so that the equivalent ratio of [amino group contained in hexamethylenediamine (HMDA)] / [HCl] was 1/1 to obtain an aqueous HMDA hydrochloride (S20).
- a mixed solution (U20) was obtained by the same composition and method as the mixed solution (U10) of Example 10 except that the EDA hydrochloride aqueous solution was changed to the HMDA hydrochloride aqueous solution (S20).
- Example 1 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 1.
- Example 10 and 21 to 23 [the ratio of the —COO— group contained in the functional group (F) neutralized with a divalent or higher-valent metal ion] (the above-mentioned ionization degree) was changed. From the results of Examples 10 and 21 to 23, in order to obtain a laminate having excellent gas barrier properties, it was confirmed that the ionization degree is preferably 60 mol% or more and 100 mol% or less, and more preferably 80 mol% or more. It was. In addition, the gas barrier laminate (Comparative Example 7) that was not ionized did not exhibit high hot water resistance and gas barrier properties.
- Example 21 the liquid mixture (U21) obtained by the same composition and method as the liquid mixture (U10) obtained in Example 10 was used.
- Example 1 Using the mixed solution (U21), coating and heat treatment were performed in the same manner as in Example 1 to obtain a laminate. Ionization was performed by immersing this laminate in a 0.1 wt% aqueous calcium acetate solution (85 ° C.) for 12 seconds. Next, this laminate was dried 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 1.
- Example 22 the liquid mixture (U22) obtained by the same composition and method as the liquid mixture (U10) obtained in Example 10 was used.
- Example 1 Using the mixed solution (U22), coating and heat treatment were performed in the same manner as in Example 1 to obtain a laminate. Ionization was performed by immersing this laminate in a 0.2 wt% calcium acetate aqueous solution (85 ° C.) for 6 seconds. Next, this laminate was dried 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 the laminate was performed in the same manner as in Example 1.
- Example 23 the liquid mixture (U23) obtained by the same composition and method as the liquid mixture (U10) obtained in Example 10 was used.
- Example 2 Using the mixed solution (U23), coating and heat treatment were performed in the same manner as in Example 1 to obtain a laminate. Ionization was performed by immersing this laminate in a 0.2 wt% aqueous calcium acetate solution (85 ° C.) for 12 seconds. Next, this laminate was dried 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 1.
- Example 6 and Example 24 confirmed the effect of using a compound (Q) containing two or more hydroxyl groups. From this, it was confirmed that the use of the compound (Q) improved the hot water resistance of the laminate, that is, the oxygen permeability after retorting, and further improved the elongation resistance, that is, the oxygen permeability after elongation.
- Example 24 A partially neutralized aqueous solution of PAA and an EDA hydrochloride aqueous solution were prepared in the same manner as in Example 1.
- polyvinyl alcohol manufactured by Kuraray Co., Ltd., PVA117 (trade name), hereinafter sometimes abbreviated as “PVA”
- PVA polyvinyl alcohol
- a mixed liquid (U24) was obtained at the same charging ratio as in Example 6 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. .
- liquid mixture (T24) obtained by the same composition and method as the liquid mixture (T6) obtained in Example 6 was diluted with 567 parts by weight of distilled water and 283 parts by weight of methanol. While stirring, 354 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight) was quickly added, and further 6.3 parts by weight of an aqueous EDA hydrochloride solution (S24) was added, followed by the above 10% by weight PVA aqueous solution. 51 parts by weight were added. In this way, a liquid mixture (U24) having a solid content concentration of 5% by weight was obtained.
- Example 10 Using the mixed solution (U24), coating, heat treatment, ionization and drying were performed in the same manner as in Example 1 to obtain a laminate (A24). 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 10.
- Example 25 the liquid mixture (U25) obtained by the same composition and method as the liquid mixture (U10) obtained in Example 10 was used. Using the mixed solution (U25), coating and heat treatment were performed in the same manner as in Example 1 to obtain a laminate. Ionization was performed by immersing this laminate in a 2 wt% magnesium acetate aqueous solution (85 ° C.) for 12 seconds. Next, this laminate was 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 the 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 (U10) obtained in Example 10 was used. Using the mixed liquid (U26), coating and heat treatment were performed in the same manner as in Example 1 to obtain a laminate. Ionization was performed by immersing this laminate in a 2 wt% zinc acetate aqueous solution (85 ° C.) for 12 seconds. Next, this laminate was dried in the same manner as in Example 1 to obtain a laminate (A26).
- Example 2 Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (26). Evaluation of the laminate and the laminate was performed in the same manner as in Example 1.
- Example 27 In contrast to Example 10, in Example 27, the surface on which the solution (U) was coated to form the gas barrier layer was changed from both surfaces of the substrate to only one surface of the substrate. From this, the gas barrier layer exists only on one side of the base material, but the gas barrier property of the resulting laminate is slightly lowered, but the Young's modulus approaches the physical property value of the base material, and the workability may be improved. It was confirmed.
- Example 27 the liquid mixture (U27) obtained by the same composition and method as the liquid mixture (U10) obtained in Example 10 was used. Coating, heat treatment, ionization and drying were carried out in the same manner as in Example 1 except that the mixed liquid (U27) was used and the coating was made only on one side to obtain a laminate (A27).
- a laminate (27) 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 laminate was performed in the same manner as in Example 10.
- the type of the substrate was changed from PET to ON. From this, it was confirmed that the use of PET as the base material has better gas barrier properties than the use of ON, and it was confirmed that PET is more suitable as the base material from the viewpoint of gas barrier properties.
- the base material of the laminated body is turned ON, the ON itself has strength, so the structure of the laminated body is changed from a three-layer structure such as a laminated body / ON / CPP to a two-layer structure such as a laminated body / CPP. Therefore, there is an advantage that it is excellent in workability.
- Example 28 the liquid mixture (U28) obtained by the same composition and method as the liquid mixture (U6) obtained in Example 6 was used. Coating, heat treatment, ionization, and drying were performed in the same manner as in Example 1 except that the mixed liquid (U28) was used and the base material was a stretched nylon film (“ON” above) to obtain a laminate (B28).
- a two-component adhesive manufactured by Mitsui Takeda Chemical Co., Ltd., A-385 (trade name) and A-50 (trade name) was coated on an unstretched polypropylene film (“CPP” above). Dried. And the film and the laminated body (B28) were laminated. Thus, a laminate (28) having a structure of 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 10.
- Example 29 In Example 29, the liquid mixture (U29) obtained by the same composition and method as the liquid mixture (U10) obtained in Example 10 was used.
- Example 28 Coating, heat treatment, ionization, and drying were performed in the same manner as in Example 28 except that the mixed solution (U29) was used to obtain a laminate (B29). Subsequently, lamination was performed in the same manner as in Example 28 to obtain a laminate (29). Evaluation of the laminate and laminate was performed in the same manner as in Example 10.
- the laminate configuration was changed from gas barrier layer / AC / ON / AC / gas barrier layer / adhesive / CPP to PET / adhesive / gas barrier layer / AC / ON / AC / gas barrier. Changed to layer / adhesive / CPP. From this, it was confirmed that there was no change in the gas barrier property even when the gas barrier laminate having ON as a base material was used in two or three layers as a laminate. Therefore, it was confirmed that the laminate structure using ON as a base material can be used as two or three layers depending on the required performance.
- Example 30 the liquid mixture (U30) obtained by the same composition and method as the liquid mixture (U6) obtained in Example 6 was used. Using the mixed solution (U30), coating, heat treatment, ionization and drying were carried out in the same manner as in Example 28 to obtain a laminate (B30).
- Example 31 In Example 31, the liquid mixture (U31) obtained by the same composition and method as the liquid mixture (U10) obtained in Example 10 was used.
- Example 28 Except for using the mixed solution (U31), coating, heat treatment, ionization, and drying were performed in the same manner as in Example 28 to obtain a laminate (B31). Subsequently, lamination was performed in the same manner as in Example 30 to obtain a laminate (31). Evaluation of the laminate and the laminate was performed in the same manner as in Example 1.
- Example 32 In contrast to Example 29, in Example 32, the surface on which the solution (U) was coated to form the gas barrier layer was changed from both surfaces of the substrate to only one surface of the substrate. From this, the gas barrier layer exists only on one side of the substrate, so that the gas barrier property of the resulting laminate is slightly lowered, but the Young's modulus approaches the physical property value of the substrate itself, and the workability may be improved. It was confirmed.
- Example 32 the liquid mixture (U32) obtained by the same composition and method as the liquid mixture (U10) obtained in Example 10 was used. Coating, heat treatment, ionization, and drying were carried out in the same manner as in Example 28 except that the mixed liquid (U32) was used and the coating was made only on one side to obtain a laminate (B32).
- Example 28 lamination was performed in the same manner as in Example 28 to obtain a laminate (32) having a structure of gas barrier layer / AC / ON / adhesive / CPP. Evaluation of the laminate was performed in the same manner as in Example 1.
- the laminates of Reference Examples 1 and 2 are each a laminate in which PET and ON are used as the base material, the compound (P) is not used, and the thickness of one coat 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 significantly different from those of the base film, and the workability is lowered, for example, the dry heat shrinkage rate is large.
- ⁇ Reference Example 1> An aqueous solution of a partially neutralized product of PAA was prepared in the same manner as in Example 1. Subsequently, the molar ratio of TMOS / GPTMOS was 89.9 / 10.1, the [inorganic component derived from TMOS and GPTMOS] / [partial neutralized product of organic component of GPTMOS and PAA] was 31.5 / A mixed solution (U33) was prepared so as to be 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 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 (the above “PET”) and dried to prepare a base material (AC (0.1 ⁇ m) / PET (12 ⁇ m)) having an anchor coat layer.
- the mixed solution (U33) was coated on the anchor coat layer of the base material with a bar coater so that the thickness after drying was 1.0 ⁇ m, and dried at 120 ° C. for 5 minutes. In the same procedure, the other side of the substrate was also coated.
- 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 ionized by immersing it in a 2% by weight calcium acetate aqueous solution (85 ° C.) for 12 seconds, and then dried at 50 ° C. for 5 minutes.
- a laminate (A33) 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 Young's modulus, and the drying heat shrinkage rate were measured by the aforementioned methods.
- Example 10 the laminate (A33) was laminated in the same manner as in Example 1 to obtain a laminate (33). Evaluation of the laminate and laminate was performed in the same manner as in Example 10.
- Example 28 lamination was performed in the same manner as in Example 28 to obtain a laminate (34). Evaluation of the laminate and laminate was performed in the same manner as in Example 10.
- a mixed liquid (U35) was obtained by the same composition and method as the mixed liquid (U33) of Reference Example 1 except that the solid content concentration was 5% by weight.
- a mixed solution (T35) prepared by the same composition and method as the mixed solution (T33) of Reference Example 1 was diluted with 542 parts by weight of distilled water and 293 parts by weight of methanol. While stirring the obtained mixed solution, 308 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight) was quickly added thereto to obtain a mixed solution (U35) having a solid content concentration of 5% by weight.
- Example 1 Using the mixed solution (U35), coating, heat treatment, ionization and drying were performed in the same manner as in Example 1 to obtain a laminate (A35). Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (35). Evaluation of the laminate and the laminate was performed in the same manner as in Example 1.
- a mixed solution (U36) was obtained by the same composition and method as the mixed solution (U35) of Comparative Example 1. Except for using the mixed solution (U36), coating, heat treatment, ionization and drying were performed in the same manner as in Example 28 to obtain a laminate (B36). Subsequently, lamination was performed in the same manner as in Example 28 to obtain a laminate (36). Evaluation of the laminate and laminate was performed in the same manner as in Example 1.
- the ratio of [equivalent of amino group contained in compound (P)] / [equivalent of —COO— group contained in functional group of polymer (X)] was 0.2 / If it is less than 100, the hot water resistance of the laminate was lowered.
- Comparative Example 4 when the above ratio was larger than 20.0 / 100, the gas barrier property of the laminate was lowered. That is, the ratio of [equivalent of amino group contained in compound (P)] / [equivalent of —COO— group contained in functional group of polymer (X)] was 0.2 / 100 to 20.0 / 100. By being in the range, it was confirmed that excellent gas barrier properties and hot water resistance were exhibited.
- ⁇ Comparative Example 3> A partially neutralized aqueous solution of PAA and an EDA hydrochloride aqueous solution were prepared in the same manner as in Example 1.
- a mixed solution (U37) was prepared at the same charging ratio as in Example 3 except that the equivalent ratio of [amino group of EDA] / [carboxyl group of PAA] was 0.1 / 100.
- a mixed solution (T37) prepared by the same composition and method as the mixed solution (T3) of Example 3 was diluted with 567 parts by weight of distilled water and 283 parts by weight of methanol.
- Example 1 Using the mixed solution (U37), coating, heat treatment, ionization and drying were performed in the same manner as in Example 1 to obtain a laminate (A37). Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (37). Evaluation of the laminate and the laminate was performed in the same manner as in Example 1.
- ⁇ Comparative example 4> A partially neutralized aqueous solution of PAA and an EDA hydrochloride aqueous solution were prepared in the same manner as in Example 1.
- a mixed solution (U38) was prepared at the same charging ratio as in Example 3 except that the equivalent ratio of [amino group of EDA] / [carboxyl group of PAA] was 29.0 / 100.
- a mixed solution (T38) prepared by the same composition and method as the mixed solution (T3) of Example 3 was diluted with 567 parts by weight of distilled water and 283 parts by weight of methanol.
- Example 1 Using the mixed solution (U38), coating, heat treatment, ionization and drying were performed in the same manner as in Example 1 to obtain a laminate (A38). Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (38). Evaluation of the laminate and the laminate was performed in the same manner as in Example 1.
- a mixed solution (U39) was prepared by changing the reaction time only in the same manner as in Comparative Example 4. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol. Subsequently, 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 were carried out at 10 ° C. for 1 hour. Reaction was performed and the liquid mixture (T39) was obtained.
- the obtained mixed liquid (T39) was diluted with 567 parts by weight of distilled water and 283 parts by weight of methanol, and then 354 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight) was rapidly added thereto while stirring. Further, 190 parts by weight of an EDA hydrochloride aqueous solution (S38) was added to obtain a mixed solution (U39) having a solid content concentration of 5% by weight.
- Example 1 Using the mixed solution (U39), coating, heat treatment, ionization and drying were performed in the same manner as in Example 1 to obtain a laminate (A39). Subsequently, lamination was performed in the same manner as in Example 1 to obtain a laminate (39). Evaluation of the laminate and the laminate was performed in the same manner as in Example 1.
- Example 1 Using the mixed solution (U40), coating and heat treatment were performed in the same manner as in Example 1 to obtain a laminate.
- the laminate was not ionized and dried.
- the laminate was laminated in the same manner as in Example 1 to obtain a laminate (40). Evaluation of the laminate and the laminate was performed in the same manner as in Example 1.
- Example 33 A partially neutralized aqueous solution of PAA and an EDA hydrochloride aqueous solution were prepared in the same manner as in Example 1. And the liquid mixture (U41) was prepared by the preparation ratio similar to Example 3 except having made the equivalent ratio of [amino group of EDA] / [carboxyl group of PAA] 20.0 / 100. Specifically, first, the mixture (T41) prepared by the same composition and method as the mixture (T3) of Example 3 was diluted with 567 parts by weight of distilled water and 283 parts by weight of methanol, and then stirred.
- 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 the 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 [equivalent of amino group contained in compound (P)] / [equivalent of -COO-group contained in functional group of polymer (X)] was 0.2.
- Examples in the range of / 100 to 20.0 / 100 exhibited high oxygen barrier properties before and after retorting. And in the comparative example whose said ratio is not in the said range, the oxygen barrier property before a retort process and / or after a retort process was low.
- the total thickness of the two gas barrier layers is 2 ⁇ m.
- the oxygen barrier property can be improved without adding the compound (P).
- workability will fall.
- Comparative Example 1 which differs from Reference Example 1 only in the thickness of the gas barrier layer, the gas barrier properties before and after the retort treatment were greatly reduced.
- the compound (P) was not added in an appropriate range, the gas barrier property was greatly lowered when the gas barrier layer was thinned.
- 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.
Abstract
Description
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、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。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。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る。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。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、2つ以上のアミノ基を含有する化合物(P)で中和および/または反応されている。さらに官能基(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。換言すれば、上記官能基の少なくとも一部が2価以上の金属イオンと塩を構成している。上記組成物において、[化合物(P)に含まれるアミノ基の当量]/[重合体(X)の官能基に含まれる-COO-基の当量]の比は、0.2/100~20.0/100の範囲にある。なお、[化合物(P)に含まれるアミノ基の当量]/[重合体(X)の官能基に含まれる-COO-基の当量]は、「化合物(P)に含まれるアミノ基のモル数]/[重合体(X)の官能基に含まれる-COO-基のモル数]と読み替えることが可能である。
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となる。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り、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である。そのため、その場合には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。
M1(OR1)qR2 p-q-rX1 r・・・(I)
[式(I)中、M1はSi、Al、Ti、Zr、Cu、Ca、Sr、Ba、Zn、Ga、Y、Ge、Pb、Sb、V、Ta、W、LaまたはNdを表す。R1はアルキル基を表す。R2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。X1はハロゲン原子を表す。pはM1の原子価と等しい。qは0~pの整数を表す。rは0~pの整数を表す。1≦q+r≦pである。]
M2(OR3)nX2 kZ2 m-n-k・・・(II)
[式(II)中、M2はSi、Al、Ti、Zr、Cu、Ca、Sr、Ba、Zn、Ga、Y、Ge、Pb、Sb、V、Ta、W、LaまたはNdを表す。R3はアルキル基を表す。X2はハロゲン原子を表す。Z2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。mはM2の原子価と等しい。nは0~(m-1)の整数を表す。kは0~(m-1)の整数を表す。1≦n+k≦(m-1)である。]
2つ以上のアミノ基を含有する化合物(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)の具体例には、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が含まれるが、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。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り、その結果、伸長された後でも高いガスバリア性を保持し、印刷、ラミネートなどの加工時のテンションによる伸長、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。
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(重合体(X))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。
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。
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EDA塩酸塩水溶液は、実施例1と同様に調製した。そして、[EDAのアミノ基]/[PAAのカルボキシル基]の当量比が1.0/100となるようにした以外は実施例1と同様の仕込み比で、混合液(U2)を調製した。具体的には、まず、実施例1の混合液(T1)と同様の組成、方法で調製した混合液(T2)を蒸留水567重量部、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、さらにEDA塩酸塩水溶液(S2)6.3重量部を加え、固形分濃度が5重量%の混合液(U2)を得た。
PAAの部分中和物水溶液およびEDA塩酸塩水溶液は、実施例1と同様に調製した。そして、実施例1と同様の仕込み比で、反応時間のみを変えて、混合液(U3)を調製した。
PAAの部分中和物水溶液およびEDA塩酸塩水溶液は、実施例1と同様に調製した。そして、[EDAのアミノ基]/[PAAのカルボキシル基]の当量比が19.4/100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(U4)を調製した。具体的には、まず、実施例3の混合液(T3)と同様の組成および方法で調製した混合液(T4)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、さらにEDA塩酸塩水溶液(S4)127重量部を加え、固形分濃度5重量%の混合液(U4)を得た。
PAAの部分中和物水溶液およびEDA塩酸塩水溶液は、実施例1と同様に調製した。そして、[EDAのアミノ基]/[PAAのカルボキシル基]の当量比が4.9/100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(U5)を調製した。具体的には、まず、実施例3の混合液(T3)と同様の組成および方法で調製した混合液(T5)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、EDA塩酸塩水溶液(S5)32重量部を加え、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EDA塩酸塩水溶液は、実施例1と同様に調製した。そして、[EDAのアミノ基]/[PAAのカルボキシル基]の当量比が1.0/100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の混合液(T3)と同様の組成、方法で調製した混合液(T6)を蒸留水567重量部、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、さらにEDA塩酸塩水溶液(S6)6.3重量部を加え、固形分濃度5重量%の混合液(U6)を得た。
PAAの部分中和物水溶液およびEDA塩酸塩水溶液は、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、[TMOS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30.0/70.0、[EDAのアミノ基]/[PAAのカルボキシル基]のモル比が1.0/100となるように、混合液(U7)を調製した。具体的には、まず、TMOS49.6重量部およびGPTMOS0.4重量部を、メタノール50重量部に溶解した。そこへ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(T7)を得た。続いて、混合液(T7)を、蒸留水566重量部およびメタノール284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%)352重量部を速やかに添加し、さらにEDA塩酸塩水溶液(S7)6.3重量部を加え、固形分濃度5重量%の混合液(U7)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7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、TMOS36重量部およびGPTMOS14重量部を、メタノール50重量部に溶解した。そこへ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(T8)を得た。続いて、混合液(T8)を、蒸留水520重量部およびメタノール301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、さらにEDA塩酸塩水溶液(S8)4.8重量部を加え、固形分濃度5重量%の混合液(U8)を得た。
TMOS/GPTMOSのモル比が89.9/10.1となるようにした以外は実施例7と同様の仕込み比で、混合液(U9)を調製した。具体的には、まず、TMOS42.6重量部およびGPTMOS7.4重量部を、メタノール50重量部に溶解した。そこへ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(T9)を得た。続いて、混合液(T9)を、蒸留水542重量部およびメタノール293重量部で希釈した後、攪拌しながらPAAの部分中和物水溶液(濃度13重量%)308重量部を速やかに添加し、さらにEDA塩酸塩水溶液(S9)5.5重量部を加え、固形分濃度5重量%の混合液(U9)を得た。
PAAの部分中和物水溶液およびEDA塩酸塩水溶液は、実施例1と同様に調製した。続いて、[TMOS]/[GPTMOS]のモル比が98.0/2.0となり、[TMOS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32.4/67.6となり、[EDAのアミノ基]/[PAAのカルボキシル基]のモル比が1.1/100となるように、混合液(U10)を調製した。具体的には、まず、TMOS48.5重量部およびGPTMOS1.5重量部を、メタノール50重量部に溶解した。そこへ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(T10)を得た。続いて、混合液(T10)を、蒸留水562重量部およびメタノール293重量部で希釈した後、攪拌しながらPAAの部分中和物水溶液(濃度13重量%)308重量部を速やかに添加し、さらにEDA塩酸塩水溶液(S10)6.2重量部を加え、固形分濃度5重量%の混合液(U10)を得た。
TMOSとGPTMOSのモル比が99.9/0.1となるようにした以外は実施例7と同様の仕込み比で、混合液(U11)を得た。具体的には、まず、TMOS49.9重量部およびGPTMOS0.1重量部を、メタノール50重量部に溶解した。そこへ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(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、さらにEDA塩酸塩水溶液(S11)6.3重量部を加え、固形分濃度5重量%の混合液(U11)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7と同様の仕込み比で、混合液(U12)を調製した。具体的には、まず、TMOS30重量部およびGPTMOS20重量部を、メタノール50重量部に溶解した。そこへ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(T12)を得た。続いて、混合液(T12)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、さらにEDA塩酸塩水溶液(S12)4.1重量部を加え、固形分濃度5重量%の混合液(U12)を得た。
PAAの部分中和物水溶液およびEDA塩酸塩水溶液は、実施例1と同様に調製した。そして、[TMOS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20.0/80.0となるようにした以外は実施例10と同様の仕込み比で、混合液(U13)を調製した。具体的には、まず、実施例10の混合液(T10)と同様の組成および方法で混合液(T13)を得た。続いて、混合液(T13)を、蒸留水842重量部およびメタノール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%)595重量部を速やかに添加し、さらにEDA塩酸塩水溶液(S13)10.6重量部を加え、固形分濃度5重量%の混合液(U13)を得た。
PAAの部分中和物水溶液およびEDA塩酸塩水溶液は、実施例1と同様に調製した。そして、[TMOS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80.0/20.0となるようにした以外は実施例10と同様の仕込み比で、混合液(U14)を調製した。具体的には、まず、実施例10の混合液(T10)と同様の組成および方法で混合液(T14)を得た。続いて、混合液(T14)を、蒸留水211重量部およびメタノール135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%)32重量部を速やかに添加し、さらにEDA塩酸塩水溶液(S14)0.6重量部を加え、固形分濃度5重量%の混合液(U14)を得た。
PAAの部分中和物水溶液およびEDA塩酸塩水溶液は、実施例1と同様に調製した。そして、[TMOS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69.9/30.1となるようにした以外は実施例10と同様の仕込み比で、混合液(U15)を得た。具体的には、まず、実施例10の混合液(T10)と同様の組成および方法で混合液(T15)を得た。続いて、混合液(T15)を、蒸留水241重量部およびメタノール148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%)59重量部を速やかに添加し、さらにEDA塩酸塩水溶液(S15)1.0重量部を加え、固形分濃度5重量%の混合液(U15)を得た。
PAAの部分中和物水溶液およびEDA塩酸塩水溶液は、実施例1と同様に調製した。そして、[TMOS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10.0/90.0となるようにした以外は実施例10と同様の仕込み比で、混合液(U16)を得た。具体的には、まず、実施例10の混合液(T10)と同様の組成および方法で混合液(T16)を得た。続いて、混合液(T16)を、蒸留水1683重量部およびメタノール766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%)1346重量部を速やかに添加し、さらにEDA塩酸塩水溶液(S16)24重量部を加え、固形分濃度5重量%の混合液(U16)を得た。
PAAの部分中和物水溶液およびEDA塩酸塩水溶液は、実施例1と同様に調製した。そして、[TMOS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90.0/10.0となるようにした以外は実施例10と同様の仕込み比で、混合液(U17)を得た。具体的には、まず、実施例10の混合液(T10)と同様の組成および方法で混合液(T17)を得た。続いて、混合液(T17)を、蒸留水188重量部およびメタノール125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%)11重量部を速やかに添加し、さらにEDA塩酸塩水溶液(S17)0.2重量部を加え、固形分濃度5重量%の混合液(U17)を得た。
[プロピレンジアミン(PDA)に含まれるアミノ基]/[HCl]の当量比が1/1となるようPDAに1N-HClを加え、PDA塩酸塩水溶液(S18)を得た。EDA塩酸塩水溶液をPDA塩酸塩水溶液(S18)に変えた以外は実施例10の混合液(U10)と同様の組成および方法で、混合液(U18)を得た。
[キトサンに含まれるアミノ基]/[HCl]の当量比が1/1となるようキトサンに1N-HClを加え、キトサン塩酸塩水溶液(S19)を得た。EDA塩酸塩水溶液をキトサン塩酸塩水溶液(S19)に変えた以外は実施例10の混合液(U10)と同様の組成および方法で、混合液(U19)を得た。
[ヘキサメチレンジアミン(HMDA)に含まれるアミノ基]/[HCl]の当量比が1/1となるようHMDAに1N-HClを加え、HMDA塩酸塩水溶液(S20)を得た。EDA塩酸塩水溶液をHMDA塩酸塩水溶液(S20)に変えた以外は実施例10の混合液(U10)と同様の組成および方法で、混合液(U20)を得た。
実施例21では、実施例10で得られた混合液(U10)と同様の組成および方法で得た混合液(U21)を使用した。
実施例22では、実施例10で得られた混合液(U10)と同様の組成および方法で得た混合液(U22)を使用した。
実施例23では、実施例10で得られた混合液(U10)と同様の組成および方法で得た混合液(U23)を使用した。
PAAの部分中和物水溶液およびEDA塩酸塩水溶液は、実施例1と同様に調製した。一方、ポリビニルアルコール(株式会社クラレ製、PVA117(商品名)、以下、「PVA」と略記する場合がある)を10重量%となるよう蒸留水に加え、85℃で3時間加熱することによってPVA水溶液を得た。
実施例25では、実施例10で得られた混合液(U10)と同様の組成および方法で得た混合液(U25)を使用した。混合液(U25)を用い、実施例1と同様にコート、熱処理を行い、積層体を得た。この積層体を2重量%の酢酸マグネシウム水溶液(85℃)に12秒間浸漬することによって、イオン化を行った。次に、この積層体を、実施例1と同様に乾燥することによって、積層体(A25)を得た。
実施例26では、実施例10で得られた混合液(U10)と同様の組成および方法で得た混合液(U26)を使用した。混合液(U26)を用い、実施例1と同様にコート、熱処理を行い、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秒間浸漬することによって、イオン化を行った。次に、この積層体を、実施例1と同様に乾燥することによって、積層体(A26)を得た。
実施例27では、実施例10で得られた混合液(U10)と同様の組成および方法で得た混合液(U27)を使用した。混合液(U27)を用いることおよびコートを片面のみに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(A27)を得た。
実施例28では、実施例6で得られた混合液(U6)と同様の組成および方法で得た混合液(U28)を使用した。混合液(U28)を用いることおよび基材を延伸ナイロンフィルム(上記「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(B28)を得た。
実施例29では、実施例10で得られた混合液(U10)と同様の組成および方法で得た混合液(U29)を使用した。
実施例30では、実施例6で得られた混合液(U6)と同様の組成および方法で得た混合液(U30)を使用した。混合液(U30)を用い、実施例28と同様にコート、熱処理、イオン化、乾燥を行い、積層体(B30)を得た。
実施例31では、実施例10で得られた混合液(U10)と同様の組成、方法で得た混合液(U31)を使用した。
実施例32では、実施例10で得られた混合液(U10)と同様の組成および方法で得た混合液(U32)を使用した。混合液(U32)を用いることおよびコートを片面のみにしたこと以外は実施例28と同様にコート、熱処理、イオン化、乾燥を行い、積層体(B32)を得た。
PAAの部分中和物の水溶液は、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、[TMOS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(U33)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。続いて、TMOSに対する水の割合が1.95モル当量となりpHが2以下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(T33)を得た。続いて、混合液(T33)を、蒸留水61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%)308重量部を速やかに添加し、固形分濃度13重量%の混合液(U33)を得た。
参考例2では、参考例1で得られた混合液(U33)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。
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の混合液(U33)と同様の組成、方法で混合液(U35)を得た。具体的には、まず、参考例1の混合液(T33)と同様の組成および方法で調製した混合液(T35)を、蒸留水542重量部およびメタノール293重量部で希釈した。得られた混合液を攪拌しながら、これにPAAの部分中和物水溶液(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(U35)を得た。
比較例1の混合液(U35)と同様の組成、方法で混合液(U36)を得た。混合液(U36)を用いること以外は実施例28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。続いて、実施例28と同様にラミネートを行い、ラミネート体(36)を得た。積層体およびラミネート体の評価については実施例1と同様に行った。
PAAの部分中和物水溶液およびEDA塩酸塩水溶液は、実施例1と同様に調製した。一方、[EDAのアミノ基]/[PAAのカルボキシル基]の当量比が0.1/100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(U37)を調製した。具体的には、まず、実施例3の混合液(T3)と同様の組成および方法で調製した混合液(T37)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。得られた混合液を攪拌しながら、これに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、さらにEDA塩酸塩水溶液(S37)0.6重量部を加え、固形分濃度5重量%の混合液(U37)を得た。
PAAの部分中和物水溶液およびEDA塩酸塩水溶液は、実施例1と同様に調製した。一方、[EDAのアミノ基]/[PAAのカルボキシル基]の当量比が29.0/100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(U38)を調製した。具体的には、まず、実施例3の混合液(T3)と同様の組成および方法で調製した混合液(T38)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。得られた混合液を攪拌しながら、これに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、さらにEDA塩酸塩水溶液(S38)190重量部を加え、固形分濃度5重量%の混合液(U38)を得た。
比較例4と同様の仕込みで反応時間のみを変えて、混合液(U39)を調製した。具体的には、まず、TMOS50重量部をメタノール50重量部に溶解した。続いて、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(T39)を得た。得られた混合液(T39)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に、攪拌しながら、これに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、さらにEDA塩酸塩水溶液(S38)190重量部を加え、固形分濃度5重量%の混合液(U39)を得た。
比較例6では、実施例10で得られた混合液(U10)と同様の組成および方法で得た混合液(U40)を使用した。
PAAの部分中和物水溶液およびEDA塩酸塩水溶液は、実施例1と同様に調製した。そして、[EDAのアミノ基]/[PAAのカルボキシル基]の当量比が20.0/100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(U41)を調製した。具体的には、まず、実施例3の混合液(T3)と同様の組成および方法で調製した混合液(T41)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、さらにEDA塩酸塩水溶液(S41)131重量部を加え、固形分濃度5重量%の混合液(U41)を得た。
Claims (16)
- 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)とを含む組成物からなり、
前記化合物(L)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(A)を含み、
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つ以上のアミノ基を含有する化合物(P)によって中和および/または反応されており、
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、
前記組成物において、[前記化合物(P)に含まれるアミノ基の当量]/[前記重合体(X)の前記官能基に含まれる-COO-基の当量]の比が0.2/100~20.0/100の範囲にあるガスバリア性積層体。 - 前記少なくとも1つの層の厚さの合計が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。 - 前記化合物(A)が、以下の式(I)で表される少なくとも1種の化合物である、請求項1に記載のガスバリア性積層体。
M1(OR1)qR2 p-q-rX1 r・・・(I)
[式(I)中、M1はSi、Al、Ti、Zr、Cu、Ca、Sr、Ba、Zn、Ga、Y、Ge、Pb、Sb、V、Ta、W、LaまたはNdを表す。R1はアルキル基を表す。R2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。X1はハロゲン原子を表す。pはM1の原子価と等しい。qは0~pの整数を表す。rは0~pの整数を表す。1≦q+r≦pである。] - 前記化合物(L)は、加水分解性を有する特性基と、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とが結合している金属原子を含む少なくとも1種の化合物(B)を含む、請求項1に記載のガスバリア性積層体。
- 前記化合物(B)が、以下の式(II)で表される少なくとも1種の化合物であり、
[前記式(I)で表される化合物に由来するM1原子のモル数]/[前記式(II)で表される化合物に由来するM2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4に記載のガスバリア性積層体。
M2(OR3)nX2 kZ2 m-n-k・・・(II)
[式(II)中、M2はSi、Al、Ti、Zr、Cu、Ca、Sr、Ba、Zn、Ga、Y、Ge、Pb、Sb、V、Ta、W、LaまたはNdを表す。R3はアルキル基を表す。X2はハロゲン原子を表す。Z2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。mはM2の原子価と等しい。nは0~(m-1)の整数を表す。kは0~(m-1)の整数を表す。1≦n+k≦(m-1)である。] - [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(P)が、エチレンジアミン、プロピレンジアミンおよびキトサンからなる群より選ばれる少なくとも1つである、請求項1に記載のガスバリア性積層体。
- 前記重合体(X)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(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)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つの官能基を含む重合体(X)と、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、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(A)を含み、
前記組成物において、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つ以上のアミノ基を含有する化合物(P)によって中和および/または反応されており、
前記組成物において、[前記化合物(P)に含まれるアミノ基の当量]/[前記重合体(X)の前記官能基に含まれる-COO-基の当量]の比が0.2/100~20.0/100の範囲にある、ガスバリア性積層体の製造方法。 - 前記化合物(L)は、加水分解性を有する特性基と、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とが結合している金属原子を含む少なくとも1種の化合物(B)を含む、請求項13に記載の製造方法。
- 前記(i)の工程は、
(i-a)前記化合物(P)と酸(R)とを含む溶液(S)を調製する工程と、
(i-b)前記化合物(L)を、加水分解、縮合して得られるオリゴマーを含む溶液(T)を調製する工程と、
(i-c)前記溶液(S)と前記溶液(T)と前記重合体(X)とを含む溶液(U)を調製する工程と、
(i-d)前記溶液(U)を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(i)の工程の後であって前記(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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JP2010143008A (ja) * | 2008-12-17 | 2010-07-01 | Kuraray Co Ltd | ラミネートチューブ容器 |
JP2011213037A (ja) * | 2010-04-01 | 2011-10-27 | Kohjin Co Ltd | ガスバリア性フィルム及び製造方法 |
JP2013010857A (ja) * | 2011-06-29 | 2013-01-17 | Kohjin Holdings Co Ltd | ガスバリア性フィルム及び製造方法 |
JP2013059930A (ja) * | 2011-09-14 | 2013-04-04 | Kohjin Holdings Co Ltd | ガスバリア性フィルム及び製造方法 |
WO2015053340A1 (ja) * | 2013-10-10 | 2015-04-16 | 東洋製罐グループホールディングス株式会社 | 水分バリア性の良好なガスバリア性積層体 |
JP2015096320A (ja) * | 2013-10-10 | 2015-05-21 | 東洋製罐グループホールディングス株式会社 | 水分バリア性の良好なガスバリア性積層体 |
US9956748B2 (en) | 2013-10-10 | 2018-05-01 | Toyo Seikan Group Holdings, Ltd. | Gas-barrier laminate having favorable water-barrier property |
US20170341352A1 (en) * | 2014-12-04 | 2017-11-30 | Mitsui Chemicals Tohcello, Inc. | Gas barrier polymer, gas barrier film, and gas barrier laminate |
KR101929142B1 (ko) | 2014-12-04 | 2018-12-13 | 미쓰이 가가쿠 토세로 가부시키가이샤 | 가스 배리어성 중합체, 가스 배리어성 필름 및 가스 배리어성 적층체 |
WO2016186074A1 (ja) * | 2015-05-18 | 2016-11-24 | 三井化学東セロ株式会社 | ガスバリア性積層体 |
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TWI711538B (zh) * | 2015-05-18 | 2020-12-01 | 日商三井化學東賽璐股份有限公司 | 氣體阻擋性積層體 |
JPWO2016186075A1 (ja) * | 2015-05-21 | 2018-03-01 | 三井化学東セロ株式会社 | ガスバリア性積層体の製造方法 |
WO2016186075A1 (ja) * | 2015-05-21 | 2016-11-24 | 三井化学東セロ株式会社 | ガスバリア性積層体の製造方法 |
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JP6365804B1 (ja) * | 2016-11-18 | 2018-08-01 | 東洋製罐グループホールディングス株式会社 | 水分吸収用積層保護フィルム |
WO2021132127A1 (ja) * | 2019-12-27 | 2021-07-01 | 三井化学東セロ株式会社 | ガスバリア用塗材、ガスバリア性フィルム、ガスバリア性積層体およびガスバリア性積層体の製造方法 |
JP2021107118A (ja) * | 2019-12-27 | 2021-07-29 | 三井化学東セロ株式会社 | ガスバリア性フィルムおよびガスバリア性積層体 |
JP7372147B2 (ja) | 2019-12-27 | 2023-10-31 | 三井化学東セロ株式会社 | ガスバリア性フィルムおよびガスバリア性積層体 |
Also Published As
Publication number | Publication date |
---|---|
ES2438987T3 (es) | 2014-01-21 |
KR20100134098A (ko) | 2010-12-22 |
KR101220103B1 (ko) | 2013-01-11 |
EP2266793B1 (en) | 2013-11-27 |
AU2009234739B2 (en) | 2012-02-09 |
CN101990494B (zh) | 2013-08-21 |
EP2266793A1 (en) | 2010-12-29 |
AU2009234739A1 (en) | 2009-10-15 |
CN101990494A (zh) | 2011-03-23 |
JPWO2009125801A1 (ja) | 2011-08-04 |
JP4486705B2 (ja) | 2010-06-23 |
US20110027581A1 (en) | 2011-02-03 |
EP2266793A4 (en) | 2013-01-23 |
US9327475B2 (en) | 2016-05-03 |
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