JP2010162865A - Pouch with spout - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pouch with a spout, which can keep oxygen-barrier properties and appearance even undergone rough handling or a harsh retort processing. <P>SOLUTION: This pouch 20 with a spout 21 is formed by using a laminate including a gas barrier layer. The gas barrier layer comprises a composition including a hydrolytic condensate of a compound (L), and a neutralized product of a polymer (X) containing a carboxy group. The compound (L) includes a compound (A) containing M<SP>1</SP>(Al, Ti or Zr) bound to a hydrolyzable characteristic group; and a compound (B) containing Si bound to a hydrolyzable characteristic group. Part of the -COO- groups in the polymer (X) is neutralized with metal ions having two or more valences. Not less than 80 mol% of the compound (B) is a compound expressed by a prescribed formula. The ratio [mole number of M<SP>1</SP>in compound (A)]/[mole number of Si atoms in compound (B)] is in the range of 0.1/99.9 to 35.0/65.0. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a pouch with a spout, for example, a pouch with a spout that is filled with a liquid or fluid food (including a beverage).

  Conventionally, liquid detergents, food liquids, and fluid foods (including liquid beverages) have been filled in rigid containers such as glass bottles, metal cans, and plastic bottles. However, these containers are expensive in packaging materials, and it is difficult to fold and discard the containers. Accordingly, plastic film pouches in which a spout portion is formed on one of the sealing surfaces have become widespread.

  The plastic film and laminated structure used for the pouch with a spout are selected according to the properties of the contents filled in the pouch. When filling contents that require quality maintenance, such as beverages, seasonings, and retort foods, it is preferable to use a laminated film including a barrier layer. As the barrier layer, an aluminum foil, a film on which an inorganic vapor deposition layer is formed, a gas barrier film, or a film in which these are laminated is used.

  Therefore, a pouch with a spout including various gas barrier layers has been proposed. For example, a pouch using a polyamide resin has been proposed (see Patent Document 1). However, the polyamide resin does not have sufficient gas barrier properties, and the gas barrier properties tend to be reduced by retort treatment.

  A spouch including a gas barrier layer made of vinylidene chloride, polyacrylonitrile, or the like has also been proposed. However, these resins have a problem that they may generate harmful substances when discarded or incinerated.

  A pouch using a laminate including a metal foil has also been proposed. However, when such a laminated body is used, there are problems that the contents cannot be visually observed through the pouch, the metal detector cannot be used at the time of inspection, and cannot be discarded as a combustible material.

  In recent years, a pouch using a laminate including an inorganic oxide vapor deposition layer such as an aluminum oxide vapor deposition layer or a silicon oxide vapor deposition layer has been proposed (see Patent Document 2). In the case of a pouch with a spout, external force (bending or impact) may be applied when filling the contents or during distribution. In a pouch with a spout using an inorganic oxide vapor deposition layer, when an external force is applied to the pouch, cracks will occur in the inorganic oxide vapor deposition layer such as the spout attachment part and the heat seal part (especially the edge part) of the pouch body. Oxygen barrier properties and water vapor barrier properties may be reduced. In addition, cracks may occur in the inorganic oxide vapor deposition layer in the vicinity of the seal portion even when the internal pressure increases due to retorting or the like after the contents are filled. Thus, when only the inorganic oxide vapor deposition layer is a gas barrier layer, a problem may arise. In order to prevent the occurrence of cracks in the inorganic oxide vapor deposition layer, it has been studied to laminate a protective layer (resin coating or film laminate) on a film including the inorganic oxide vapor deposition layer (Patent Document 3).

  A pouch formed using a transparent gas barrier laminate that can be retorted has also been proposed (Patent Document 4). The gas barrier layer of the gas barrier laminate is formed by applying a water-soluble paint to a plastic substrate.

  On the other hand, the present inventors have proposed a pouch with a spout capable of performing retort processing at high temperature with little reduction in gas barrier properties due to bending or impact during filling or transportation of contents (Patent Document 5).

Japanese Patent No. 3940250 Japanese Patent No. 3923582 JP-A-10-29263 JP 2005-144760 A JP 2007-8149 A

  The pouch of Patent Document 5 shows high oxygen barrier properties even after retorting, after transportation, and after long-term storage. However, a pouch with a spout is often exposed to severe bending or impact for the purpose of containing liquid or liquid food, and further improvement of durability of the gas barrier layer against bending or impact is required. By making the gas barrier layer thin, it is possible to improve the durability of the gas barrier layer against bending and impact. However, in the gas barrier laminate of Patent Document 5, when the gas barrier layer is thinned, the oxygen barrier property may be greatly reduced.

  Also, when pouches with spouts are arranged on a thin tray and retort processing is performed, the retort processing is performed in a state where the pouches with spouts are in close contact with each other. In order to perform heat sterilization, retort processing under severe conditions may be required. For this reason, a pouch with a spout is required to have higher retort resistance. Specifically, it is required to maintain high oxygen barrier properties and transparency even after retorting treatment under harsh conditions. However, in the pouch of Patent Document 5, when the retort treatment is performed under severe conditions, the transparency may be lowered.

  In such a situation, an object of the present invention is to provide a spout with a spout that can maintain oxygen barrier properties and appearance even after severe handling and severe retort processing.

  As a result of intensive studies to achieve the above object, the present inventors have used a gas barrier laminate including a gas barrier layer made of a specific composition, so that even if harsh handling or harsh retort treatment is performed, oxygen It has been found that a pouch with a spout that can maintain the barrier properties and appearance can be obtained. The present invention is based on this novel finding.

The pouch with a spout of the present invention is a pouch with a spout formed using a gas barrier laminate. The gas barrier laminate includes a base material and at least one layer having gas barrier properties laminated on the base material. The layer comprises a hydrolysis condensate of at least one compound (L) containing a hydrolyzable characteristic group, and a polymer containing at least one functional group selected from a carboxyl group and a carboxylic anhydride group. It consists of a composition containing the neutralized product of (X). The compound (L) includes a compound (A) and a compound (B) containing Si to which a hydrolyzable characteristic group is bonded. The compound (A) is at least one compound represented by the following formula (I).
^{_{M 1 X 1 m Y 1 nm}} ··· (I)
[In Formula (I), M ¹ represents any one selected from Al, Ti, and Zr. X ¹ represents any one selected from F, Cl, Br, I, OR ¹ , R ² COO, R ³ COCHCOR ⁴ , and NO ₃ . Y ¹ represents any one selected from F, Cl, Br, I, OR ⁵ , R ⁶ COO, R ⁷ COCHCOR ⁸ , NO ₃ and R ⁹ . R ¹ , R ² , R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group. R ³ , R ⁴ , R ⁷ , R ⁸ and R ⁹ each independently represents an alkyl group. n is equal to the valence of M ¹ . m represents an integer of 1 to n. ]

The compound (B) includes at least one compound represented by the following formula (II).
Si (OR ¹⁰ ) _p R ¹¹ _4-pq X ² _q (II)
[In the formula (II), R ¹⁰ represents an alkyl group. R ¹¹ represents an alkyl group, an aralkyl group, an aryl group or an alkenyl group. X ² represents a halogen atom. p and q represent the integer of 0-4 each independently. 1 ≦ p + q ≦ 4. ]

At least a part of the —COO— group contained in the functional group of the polymer (X) is neutralized with a divalent or higher valent metal ion. The proportion of the compound represented by the formula (II) in the compound (B) is 80 mol% or more. In the composition, a ratio of [number of moles of the M ¹ atom derived from the compound (A)] / [number of moles of Si atom derived from the compound (B)] is 0.1 / 99.9 to 35. It is in the range of 0.0 / 65.0.

  According to the present invention, it is possible to obtain a pouch with a spout capable of maintaining the oxygen barrier property and the appearance even when harsh handling or harsh retorting is performed. The pouch of the present invention can be subjected to retort (pressurized hot water) treatment at a high temperature for sterilization. By using the pouch of the present invention, it is possible to prevent the contents from being altered by oxygen even before retorting, during retorting, after retorting, after transportation, and after long-term storage. In addition, since the pouch of the present invention has good transparency, it is easy to check the contents and the deterioration of the contents due to deterioration.

It is a perspective view which shows an example of the pouch with a spout of this invention. It is a perspective view which shows another example of the pouch with a spout of this invention.

  Embodiments of the present invention will be described below. In the following description, a specific compound may be exemplified as a substance that exhibits a specific function, but the present invention is not limited to this. In addition, the materials exemplified may be used alone or in combination unless otherwise specified.

  The pouch with a spout of the present invention is formed by using a specific laminate (hereinafter sometimes referred to as “gas barrier laminate”). That is, the pouch with a spout of the present invention includes a gas barrier laminate. Note that all of the pouches may be formed using the gas barrier laminate, or a part thereof may be formed of a material other than the gas barrier laminate. For example, the gas barrier laminate is used for 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 100% of the area of the pouch.

  The pouch with a spout of the present invention can be produced, for example, by stacking gas barrier laminates and heat-sealing the gas barrier laminate together with spouts (spouts). There is no restriction | limiting in particular in the shape of a pouch, For example, a flat pouch, a pillow packaging bag, a 4-way seal bag, a 3-way seal bag, a gusset-shaped bag, a standing pouch etc. may be sufficient. As an example of the pouch with a spout of the present invention, a perspective view of a standing type pouch 10 with a spout is shown in FIG. 1, and a perspective view of a pillow type pouch 20 with a spout is shown in FIG. Spouted pouches 10 and 20 include spouts 11 and 21, respectively.

Hereinafter, the gas barrier laminate used in the present invention will be described in detail.
[Gas barrier laminate]
The gas barrier laminate used in the present invention includes a substrate and at least one layer having gas barrier properties laminated on the substrate. The layer (hereinafter sometimes referred to as “gas barrier layer”) is made of a specific composition. The composition comprises a hydrolyzate condensate of at least one compound (L) containing a hydrolyzable characteristic group and at least one functional group selected from a carboxyl group and a carboxylic anhydride group. And a neutralized product of the combined (X). The compound (L) is at least one compound containing a hydrolyzable characteristic group, and is typically at least one compound containing a metal atom to which the hydrolyzable characteristic group is bonded. . The compound (L) includes a compound (A) and a compound (B) containing Si to which a hydrolyzable characteristic group is bonded. Hereinafter, at least one functional group selected from a carboxyl group and a carboxylic anhydride group contained in the polymer (X) may be referred to as “functional group (F)”. At least a part of the —COO— group contained in the functional group (F) is neutralized with a divalent or higher valent metal ion. From another viewpoint, the —COO— group contained in the functional group (F) constitutes a salt with a divalent or higher metal ion.

  The gas barrier layer is laminated on at least one surface of the substrate. A gas barrier layer may be laminated | stacked only on the single side | surface of a base material, and may be laminated | stacked on both surfaces of a base material. The gas barrier laminate used in the present invention may include layers other than the gas barrier layer.

  The proportion of the hydrolyzed condensate of compound (L) and the neutralized product of polymer (X) in the composition is, for example, 50% by weight, 70% by weight, 80% by weight, 90% by weight, 95% by weight. % Or more, or 98% by weight or more.

[Hydrolysis condensate]
The composition which comprises a gas barrier layer contains the hydrolysis-condensation product of a compound (L). By hydrolyzing the compound (L), at least a part of the characteristic group of the compound (L) is substituted with a hydroxyl group. Furthermore, the hydrolyzate condenses to form a compound in which metal atoms are bonded through oxygen. When this condensation is repeated, a compound that can be substantially regarded as a metal oxide is formed. Here, in order for this hydrolysis and condensation to occur, it is important that the compound (L) contains a hydrolyzable characteristic group (functional group). When those groups are not bonded, hydrolysis / condensation reaction does not occur or becomes extremely slow, and it is difficult to obtain the effects of the present invention. Si may be classified as a metalloid element, but in this specification, Si is described as a metal.

  This hydrolysis-condensation product can be manufactured from a specific raw material using the method used by the well-known sol-gel method, for example. 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. Although there is no particular limitation, for example, a condensate obtained by hydrolysis and condensation of about 2 to 10 molecules can be used as a raw material. Specifically, for example, a material obtained by hydrolyzing and condensing tetramethoxysilane into a dimer to 10-mer linear condensate can be used as a raw material.

Compound (A) is at least one compound represented by the following formula (I).
M ¹ X ¹ _m Y ¹ _nm (I)
[In Formula (I), M ¹ represents any one selected from Al, Ti, and Zr. X ¹ represents any one selected from F, Cl, Br, I, OR ¹ , R ² COO, R ³ COCHCOR ⁴ , and NO ₃ . Y ¹ represents any one selected from F, Cl, Br, I, OR ⁵ , R ⁶ COO, R ⁷ COCHCOR ⁸ , NO ₃ and R ⁹ . R ¹ , R ² , R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group. R ³ , R ⁴ , R ⁷ , R ⁸ and R ⁹ each independently represents an alkyl group. n is equal to the valence of M ¹ . m represents an integer of 1 to n. ]

X ¹ and Y ¹ may be the same or different. M ¹ is preferably Al from the viewpoint of particularly reducing changes in appearance such as oxygen barrier properties and transparency before and after retorting of the obtained gas barrier laminate. X ¹ is a group having hydrolyzability. X ¹ is preferably any one selected from Cl, OR ¹ , and NO ₃ , and more preferably OR ¹ . Y ¹ is preferably any one selected from Cl, OR ⁵ , and NO ₃ , and more preferably OR ⁵ .

The carbon number of the alkyl group used for R ¹ , R ² , R ⁵ and R ⁶ is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, for example 1 or more and 4 or less. R ¹ and R ⁵ are preferably a methyl group, an ethyl group, an iso-propyl group, an n-butyl group, or a t-butyl group, and particularly preferably an iso-propyl group or an n-butyl group. The number of carbon atoms of the alkyl group used for R ³ , R ⁴ , R ⁷ , R ⁸ and R ⁹ is preferably 1 or more and 4 or less, more preferably 1 or more and 2 or less. R ³ , R ⁴ , R ⁷ and R ⁸ are preferably a methyl group or an ethyl group. R ³ COCHCOR ⁴ and R ⁷ COCHCOR ⁸ can be coordinated to atom M ¹ at the carbonyl group. R ⁹ is preferably a methyl group or an ethyl group. R ⁹ usually does not have a functional group. In the formula (I), [nm] may be 0 or 1, for example.

  Specific examples of the compound (A) include aluminum chloride, aluminum triethoxide, aluminum trinormal propoxide, aluminum triisopropoxide, aluminum trinormal butoxide, aluminum tri-t-butoxide, aluminum triacetate, aluminum acetylacetonate, nitric acid Aluminum compounds such as aluminum; titanium compounds such as titanium tetraisopropoxide, titanium tetranormal butoxide, titanium tetra (2-ethylhexoxide), titanium tetramethoxide, titanium acetylacetonate, titanium ethylacetoacetate; zirconium tetranormal Zirconium compounds such as propoxide, zirconium tetrabutoxide, zirconium tetraacetylacetonate and the like are included. Preferable examples of compound (A) include aluminum triisopropoxide and aluminum trinormal butoxide.

The compound (B) is at least one Si compound containing Si to which a hydrolyzable characteristic group is bonded. The compound (B) includes at least one compound represented by the following formula (II).
Si (OR ¹⁰ ) _p R ¹¹ _4-pq X ² _q (II)
[In the formula (II), R ¹⁰ represents an alkyl group. R ¹¹ represents an alkyl group, an aralkyl group, an aryl group or an alkenyl group. X ² represents a halogen atom. p and q represent the integer of 0-4 each independently. 1 ≦ p + q ≦ 4. ]

The alkyl group R ¹⁰ represents a methyl group, an ethyl group, n- propyl group, iso- propyl, n- butyl group, etc. t- butyl group, preferably a methyl group or an ethyl group. Examples of the halogen atom represented by X ² include a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable. Examples of the alkyl group represented by R ¹¹ include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a t-butyl group, and an n-octyl group. As the aralkyl group, For example, benzyl group, phenethyl group, trityl group and the like can be mentioned. In addition, examples of the aryl group represented by R ¹¹ include a phenyl group, a naphthyl group, a tolyl group, a xylyl group, and a mesityl group. Examples of the alkenyl group include a vinyl group and an allyl group.

  Specific examples of the compound (B) represented by the formula (II) include tetrachlorosilane, tetrabromosilane, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, octyltrimethoxysilane, phenyltri Methoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, chlorotrimethoxysilane, chlorotriethoxysilane, dichlorodimethoxysilane, dichlorodiethoxysilane, trichloromethoxysilane, trichloroethoxysilane, and vinyltrichlorosilane are included. Preferred examples of the compound (B) represented by the formula (II) include tetramethoxysilane and tetraethoxysilane.

Compound (B) may further contain at least one compound represented by the following formula (III) in addition to the compound represented by formula (II). By including the compound represented by the formula (III), changes in oxygen barrier properties and changes in appearance such as transparency before and after the boil treatment and before and after the retort treatment are further reduced.
Si (OR ¹² ) _r X ³ _s Z ³ _4-rs (III)
[In the formula (III), R ¹² represents an alkyl group. X ³ represents a halogen atom. Z ³ represents an alkyl group substituted with a functional group having reactivity with a carboxyl group. r and s each independently represent an integer of 0 to 3. 1 ≦ r + s ≦ 3. ]

Is, for example, methyl group as the alkyl group represented by R ^12, ethyl group, n- propyl group, iso- propyl, n- butyl group, etc. t- butyl group, preferably a methyl group or an ethyl group. Examples of the halogen atom represented by X ³ include a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable. Examples of the functional group having reactivity with a carboxyl group that Z ³ has include an epoxy group, an amino group, a hydroxyl group, a halogen atom, a mercapto group, an isocyanate group, a ureido group, an oxazoline group, and a carbodiimide group. Among these, an epoxy group, an amino group, an isocyanate group, a ureido group, or a halogen atom is present from the viewpoint of particularly reducing changes in appearance such as oxygen barrier properties and transparency before and after retorting of the obtained gas barrier laminate. Preferably, for example, at least one selected from an epoxy group, an amino group, and an isocyanate group may be used. Examples of the alkyl group substituted with such a functional group include those exemplified for R ¹² .

  Specific examples of the compound represented by the formula (III) include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrichlorosilane, γ-aminopropyltrisilane. Methoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltrichlorosilane, γ-bromopropyltrimethoxysilane, γ -Bromopropyltriethoxysilane, γ-bromopropyltrichlorosilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltrichlorosilane, γ-isocyanatopropyltrimethoxysilane , .Gamma. isocyanatopropyltriethoxysilane, .gamma. isocyanate propyl trichlorosilane, .gamma.-ureidopropyltrimethoxysilane, .gamma.-ureidopropyltriethoxysilane include .gamma. ureidopropyltrimethoxysilane trichlorosilane. Preferred examples of the compound represented by the formula (III) include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-chloropropyltrimethoxysilane, and γ-chloropropyltriethoxysilane. , Γ-aminopropyltrimethoxysilane, and γ-aminopropyltriethoxysilane.

  The inventors have obtained a gas barrier laminate obtained by using a hydrolysis condensate of the compound (L) containing the compound (A) and the compound (B), which has excellent gas barrier properties, boil resistance, It has been found that it exhibits hot water resistance such as retort resistance. That is, it has been found that the gas barrier laminate not only has excellent gas barrier properties but also maintains excellent gas barrier properties even after being subjected to boil treatment or retort treatment, and there is no change in appearance. Furthermore, surprisingly, in the gas barrier laminate, as described above, when the gas barrier layer is thinned, the gas barrier property is decreased exponentially and the excellent gas barrier property cannot be maintained. It was newly found that by using the hydrolysis condensate of L), a high gas barrier property can be maintained even if the gas barrier layer is thinned.

In any case where the compound (B) is composed only of the compound of the formula (II) and the compound (B) contains the compound of the formula (III), [the M ¹ atom derived from the compound (A) The ratio of [number of moles] / [number of moles of Si atoms derived from compound (B)] is 0.1 / 99.9 to 35.0 / 65.0 (for example, 0.1 / 99.9 to 30.0). /70.0, or 0.1 / 99.9 to 29.9 / 70.1). When the above molar ratio is in this range, a gas barrier laminate exhibiting excellent gas barrier properties, hot water resistance such as boil resistance and retort resistance as described above can be obtained. When the ratio of M ¹ to the total of M ¹ and Si is lower than 0.1 mol%, the hot water resistance is lowered, the gas barrier property after retort treatment is lowered, and an appearance defect may occur. Moreover, when the ratio is higher than 35 mol%, there is a problem that gas barrier properties before and after the retort treatment are lowered. Further, from the viewpoint of better gas barrier properties and retort resistance, the ratio of [number of moles of M ¹ atom derived from compound (A)] / [number of moles of Si atom derived from compound (B)] is preferably Is in the range of 1.2 / 98.8 to 30.0 / 70.0, more preferably in the range of 1.9 / 98.1 to 30.0 / 70.0, and even more preferably 2.8. /97.2 to 30.0 / 70.0. The ratio is in the range of 0.5 / 99.5 to 30.0 / 70.0, in the range of 1.5 / 98.5 to 20.0 / 80.0, or 2.5 / 97.5 to 10 It may be in the range of 0.0 / 90.0.

  The present inventors use, in addition to the compound represented by the compound (A) and the formula (II), a hydrolysis condensate of the compound (L) further comprising a compound represented by the formula (III), It has been found that the gas barrier laminate exhibits further excellent gas barrier properties and hot water resistance such as boil resistance and retort resistance.

  In the case where the compound (B) contains a compound represented by the formula (III), it is preferable that the following conditions are further satisfied. That is, the ratio of [number of moles of Si derived from the compound represented by formula (II)] / [number of moles of Si derived from the compound represented by formula (III)] was 99.5 / 0.5 to It is preferably in the range of 80.0 / 20.0. If this ratio is greater than 99.5 / 0.5, the resulting gas barrier laminate has properties that do not change its appearance such as gas barrier properties and transparency before and after boiling and retorting, that is, hot water resistance decreases. There is a case. Moreover, when this ratio is smaller than 80/20, the gas barrier property of the gas barrier laminate obtained may deteriorate. Further, this ratio is more preferably in the range of 98.0 / 2.0 to 89.9 / 10.1 from the viewpoint of better hot water resistance and gas barrier properties of the gas barrier laminate.

  The total ratio of the compound (A) and the compound (B) in the compound (L) is, for example, 80 mol% or more and 100 mol% or less, 90 mol% or more, 95 mol% or more, 98 mol% or more, 99 It may be mol% or more, or 100 mol%.

  The proportion of the compound represented by the formula (II) in the compound (B) (Si compound as the compound (L)) is 80 mol% or more and 100 mol% or less, for example, 90 mol% or more, 95 mol% or more. 98 mol% or more, or 100 mol%. In one example, the compound (B) consists only of the compound represented by the formula (II), and in another example, the compound (B) is represented by the compound represented by the formula (II) and the formula (III). It consists only of a compound.

  The number of molecules condensed in the hydrolyzed condensate of compound (L) can be controlled by the conditions for performing hydrolysis and condensation. For example, the number of molecules to be condensed can be controlled by the amount of water, the type and concentration of the catalyst, the temperature at which hydrolysis condensation is performed, and the like.

  Since the gas barrier property of the composition constituting the gas barrier layer becomes better, [weight of inorganic component derived from compound (L)] / [weight of organic component derived from compound (L)] The ratio of the “total with 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, and 30.5 / 69.5 More preferably, it is in the range of 70/30.

  The weight of the inorganic component derived from the compound (L) can be calculated from the weight of the raw material used when preparing the composition. That is, compound (L), compound (L) partially hydrolyzed, compound (L) completely hydrolyzed, compound (L) partially hydrolyzed, compound (L) Assuming that the product is completely hydrolyzed and partly condensed, or a combination of these, is completely hydrolyzed and condensed into a metal oxide, and the weight of the metal oxide is calculated as compound (L). It is regarded as the weight of the inorganic component derived from.

More specifically describing the calculation of the weight of the metal oxide, when the compound (A) represented by the formula (I) does not contain R ⁹ , when it is completely hydrolyzed and condensed, the composition formula is a compound represented by M ¹ O n _{/ 2.} In addition, when the compound (A) represented by the formula (I) contains R ⁹ , when it is completely hydrolyzed / condensed, the compound represented by the formula M ¹ O _{m / 2} R ⁹ _nm It becomes. Of this compound, the M ¹ O _{m / 2} portion is a metal oxide. R ⁹ is an organic component derived from the compound (L). Moreover, it calculates similarly about a compound (B). At this time, R ¹¹ and Z ³ are organic components derived from the compound (L). The value obtained by dividing the weight of the metal oxide by the weight of the active ingredient added until the end of the step (i) described later and multiplying the value by 100 is the content (%) of the hydrolysis condensate in this specification. It is. Here, the weight of the active ingredient refers to a compound or solvent generated in the process in which the above-described compound (L) is converted into a metal oxide from the weight of all the ingredients added until the end of the step (i) described later. This is the weight excluding the weight of volatile components.

  When the polymer (X) is neutralized by ions not containing metal ions (for example, ammonium ions), the weight of the ions (for example, ammonium ions) is also the weight of the organic component derived from the polymer (X). Added to.

[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. Hereinafter, the polymer may be referred to as “carboxylic acid-containing polymer”. The neutralized product of the carboxylic acid-containing polymer can be obtained by neutralizing at least 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. Moreover, the polymer containing the structural unit which has the structure of carboxylic anhydrides, such as a maleic anhydride unit and a phthalic anhydride unit, can also be used. One type or two types of structural units having one or more carboxyl groups and / or structural units having a structure of carboxylic anhydride (hereinafter, these may be collectively referred to as “carboxylic acid-containing units (G)”) The above may be contained in the carboxylic acid-containing polymer.

  Moreover, the gas barrier property laminated body with favorable gas barrier property is obtained by making the content rate of the carboxylic acid content unit (G) which occupies for all the structural units of a carboxylic acid containing polymer into 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. In addition, when 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. When 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.

  Specific examples of the carboxylic acid-containing polymer 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 in the case of containing other structural units other than the above-described carboxylic acid-containing unit (G) include ethylene-maleic anhydride copolymers, styrene-maleic anhydride copolymers, and isobutylene-maleic anhydride. Examples thereof include an alternating copolymer, an ethylene-acrylic acid copolymer, and a saponified ethylene-ethyl acrylate copolymer.

  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.

  Further, although 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 weight average molecular weight / number average molecular weight ratio of the carboxylic acid-containing polymer is preferably in the range of 1-6, more preferably in the range of 1-5, and in the range of 1-4. More preferably.

[Neutralization (ionization)]
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.

  It is important that the metal ion neutralizing the functional group (F) is divalent or higher. When the functional group (F) is not neutralized or neutralized only by monovalent ions, a laminate having good gas barrier properties cannot be obtained. Specific examples of 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. For example, 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.

  For example, 10 mol% or more (for example, 15 mol% or more) of the —COO— group contained in the functional group (F) of the carboxylic acid-containing polymer is neutralized with a divalent or more metal ion. When 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 exhibits good gas barrier properties.

  Note that 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 anhydride groups, the total number of —COO— groups contained is (a + 2b) moles. The proportion of the -COO- group contained in the functional group (F) that 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 infrared absorption spectrum peak attributed to C = O stretching vibration of the carboxyl group or carboxylic anhydride group before the neutralization (ionization front) is observed in the range of 1600cm ^-1 ~1850cm ^-1, neutralization (ionization ), The C═O stretching vibration of the carboxyl group is observed in the range of 1500 cm ^{−1 to} 1600 cm ⁻¹ , so that both can be separated and evaluated in the infrared absorption spectrum. Specifically, the ratio is obtained from the maximum absorbance in each range, and the ionization degree of the polymer constituting the gas barrier layer in the gas barrier laminate can be calculated using a calibration curve prepared in advance. A calibration curve can be created by measuring infrared absorption spectra for a plurality of standard samples having different degrees of neutralization.

  When the film thickness of the gas barrier layer is 1 μm or less and the substrate contains an ester bond, the ester bond peak of the substrate is detected in the infrared absorption spectrum by the ATR method, and the carboxylic acid-containing polymer constituting the gas barrier layer Since it overlaps with the —COO— peak of (= polymer (X)), the degree of ionization cannot be determined accurately. Therefore, the ionization degree of the polymer (X) constituting the gas barrier layer having a thickness of 1 μm or less is calculated based on the result of the fluorescent X-ray measurement.

  Specifically, 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. Next, 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. Then, 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. And X-ray fluorescence measurement is performed about the gas-barrier laminated body using the base material containing an ester bond, and an ionization degree is calculated | required based on the said calibration curve from the fluorescence X-ray intensity of the metal element used for ionization.

[Compound (P)]
The composition constituting the gas barrier layer may contain a compound (P) containing two or more amino groups. Compound (P) is a compound different from compound (L) and polymer (X). When the compound (P) is further included, at least a part of the —COO— group contained in the functional group (F) of the polymer (X) is neutralized and / or reacted with the compound (P); Become. As the compound (P), alkylene diamines, polyalkylene polyamines, alicyclic polyamines, aromatic polyamines, polyvinylamines, and the like can be used, but the gas barrier property of the gas barrier laminate is improved. Therefore, alkylene diamine is preferable.

  Specific examples of the compound (P) include hydrazine, ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, diaminodiphenylmethane, 1,3-diaminocyclohexane, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane. , Xylylenediamine, chitosan, polyallylamine, polyvinylamine and the like. From the viewpoint of improving the gas barrier properties of the gas barrier laminate, ethylenediamine, propylenediamine, and chitosan are preferable.

  The molar ratio of [amino group contained in compound (P)] / [-COO-group contained in functional group of carboxylic acid-containing polymer] is 0 from the viewpoint of improving the hot water resistance of the gas barrier laminate. It is preferably in the range of 2/100 to 20/100, more preferably in the range of 0.5 / 100 to 15/100, and particularly preferably in the range of 1/100 to 10/100.

  When adding the compound (P) to the carboxylic acid-containing polymer, the compound (P) may be neutralized with an acid in advance. Examples of the acid used for neutralization include hydrochloric acid, nitric acid, sulfuric acid, acetic acid, and carbonic acid. From the viewpoint of better gas barrier properties of the resulting gas barrier laminate, it is preferable to use hydrochloric acid, acetic acid, and carbonic acid.

[Compound Q]
The composition constituting the gas barrier layer may contain a compound (Q) containing two or more hydroxyl groups. When the compound (Q) is further included, at least a part of the —COO— group contained in the functional group (F) of the polymer (X) reacts with the compound (Q) to form an ester bond. It becomes. According to this configuration, the gas barrier property after elongation of the gas barrier laminate is improved. More specifically, by adding the compound (Q), the gas barrier layer is hardly damaged even when the gas barrier laminate is elongated. As a result, high gas barrier properties are maintained even after being stretched. For example, the gas barrier property of the gas barrier laminate is unlikely to deteriorate even in a state after elongation due to tension during processing such as printing or laminating or elongation when a pouch 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, and starches. Polymer compounds such as polysaccharide derivatives derived from saccharides are included.

  Further, the 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 material]
As the base material used in the gas barrier laminate, base materials made of various materials such as a thermoplastic resin film and a thermosetting resin film can be used. For example, a film having a predetermined shape made of a film such as a thermoplastic resin film or a thermosetting resin film; a fiber aggregate such as fabric or paper; wood; a metal oxide or the like can be used. Especially, 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. The base material may have a multilayer structure composed of a plurality of materials.

  Examples of the thermoplastic resin film 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. As the base material of the laminate used for the food packaging material, 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 is a stretched film, particularly a biaxially stretched film because it has excellent processability for printing, laminating and the like of a gas barrier laminate. It is 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.

  Further, the gas barrier laminate may further include an adhesive layer (H) disposed between the base material and the gas barrier layer. According to this structure, the adhesiveness of a base material and a gas barrier layer can be improved. 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. As a result of examining various adhesive resins, it is preferable that 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 a range of 0.5 to 12% by weight. It was found. By using such an adhesive resin, the adhesion between the substrate and the gas barrier layer can be particularly enhanced. By strongly bonding the base material and the gas barrier layer through the adhesive layer (H), it is possible to suppress deterioration of the gas barrier property and appearance when the gas barrier laminate is subjected to processing such as printing or lamination. . 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.

  As the adhesive resin containing a urethane bond, a two-component reactive polyurethane adhesive in which a polyisocyanate component and a polyol component are mixed and reacted is preferable.

  By increasing the thickness of the adhesive layer (H), the strength of the gas barrier laminate can be increased. However, when the adhesive layer (H) is too thick, the appearance deteriorates. The thickness of the adhesive layer (H) is preferably in the range of 0.03 μm to 0.18 μm. According to this configuration, when processing such as printing or laminating is performed on the gas barrier laminate, it is possible to suppress deterioration of the gas barrier properties and appearance, and further, the drop strength of the packaging material using the gas barrier laminate. Can be increased. The thickness of the adhesive layer (H) is more preferably in the range of 0.04 μm to 0.14 μm, and still more preferably in the range of 0.05 μm to 0.10 μm.

In the gas barrier laminate used in the present invention, the total thickness of the gas barrier layers contained in the laminate is preferably 1.0 μm or less, for example 0.9 μm or less. By making the gas barrier layer thin, the dimensional change of the gas barrier laminate during processing such as printing and laminating can be kept low, and the flexibility of the gas barrier laminate is further increased. It is possible to approximate the mechanical properties of the film itself used. In the gas barrier laminate used in the present invention, even when the total thickness of the gas barrier layers contained in the laminate is 1.0 μm or less (for example, 0.9 μm or less), oxygen permeation in an 85% RH atmosphere at 20 ° C. The degree can be set to 1.1 cm ³ / (m ² · day · atm) or less (for example, 1.0 cm ³ / (m ² · day · atm) or less). The thickness of one gas barrier layer is preferably 0.05 μm or more (for example, 0.15 μm or more) from the viewpoint of improving the gas barrier property of the gas barrier laminate. Further, the total thickness of the gas barrier layer is more preferably 0.1 μm or more (for example, 0.2 μm 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.

  In addition, 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 which comprises an inorganic layer should just have gas barrier property with respect to oxygen, water vapor | steam, etc., Preferably it has transparency. For example, 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. Among these, 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.

  Although the preferable thickness of an inorganic layer changes with kinds of inorganic oxide which comprises an inorganic layer, it is the range of 2 nm-500 nm normally. 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 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 to 200 nm, more preferably in the range of 10 to 100 nm.

  The inorganic layer can be formed by depositing an inorganic oxide on the substrate. Examples of the forming method include a vacuum deposition method, a sputtering method, an ion plating method, a chemical vapor deposition method (CVD), and the like. Among these, the vacuum evaporation method is preferably used from the viewpoint of productivity. As 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. Moreover, in order to improve the adhesiveness of an inorganic layer and a base material, and the denseness of an inorganic layer, you may vapor-deposit using a plasma assist method or an ion beam assist method. Moreover, in order to raise the transparency of an inorganic layer, you may employ | adopt the reactive vapor deposition method which blows in oxygen gas etc. and produces a reaction in the case of vapor deposition.

  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 (α) and an island phase (β). The island phase (β) is a region where the ratio of the hydrolysis condensate of the compound (L) is higher than that of the sea phase (α).

  Each of the sea phase (α) and the island phase (β) preferably further has a fine structure. For example, the sea phase (α) is composed of a sea phase (α1) mainly composed of a neutralized product of a carboxylic acid-containing polymer and an island phase (α2) mainly composed of a hydrolysis condensate of the compound (L). The sea island structure to be formed may be further formed. The island phase (β) is composed of a sea phase (β1) mainly composed of a neutralized product of a carboxylic acid-containing polymer and an island phase (β2) 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 (β2) / sea phase (β1)] in the island phase (β) is the ratio of [island phase (α2) / sea phase (α1)] in the sea phase (α). Is preferably larger. The diameter of the island phase (β) 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 (α2) and the island phase (β2) is preferably 50 nm or less, more preferably 30 nm or less, and even more preferably 20 nm or less.

  In order to obtain the structure as described above, it is necessary that the appropriate hydrolysis condensation of the compound (L) occurs in preference to the crosslinking reaction between the compound (L) and the carboxylic acid-containing polymer. For this purpose, 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.

  Moreover, when specific manufacturing conditions were selected, it was found that a region where the ratio of the hydrolysis condensate of compound (L) is high is formed in a layered manner on the surface of the gas barrier layer. Hereinafter, 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”. 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. Surprisingly, even when a skin layer having hydrophobic characteristics is formed on the surface of the gas barrier layer, the wettability of the printing ink or the like to the surface is good. The presence or absence of the skin layer of the gas barrier layer or the state of the formed skin layer varies depending on the production conditions. As a result of intensive studies, 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 formation of the skin layer may be insufficient. In this case, 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. Further, when 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. On the other hand, when the contact angle is larger than 65 °, the skin layer becomes too thick and the transparency of the gas barrier laminate is lowered. Therefore, the contact angle is preferably 65 ° or less, more preferably 60 ° or less, and still more preferably 58 ° or less.

  The gas barrier laminate may further include a polyolefin layer (hereinafter sometimes referred to as “PO layer”) laminated on the substrate. The “lamination on the substrate” includes not only the case of being laminated directly on the substrate but also the case of being laminated on the substrate via another layer. For example, a PO layer may be used for the inner layer of the layer constituting the gas barrier laminate in order to impart heat sealability. Hereinafter, the multilayer film including the base material and the gas barrier layer formed on the base material may be referred to as a gas barrier multilayer film. This gas barrier multilayer film is also a kind of gas barrier laminate.

  The gas barrier laminate may include a layer for imparting various characteristics (for example, heat sealability). The gas barrier laminate may have a structure of surface layer / PO layer, surface layer / intermediate layer / PO layer, surface layer / intermediate layer / intermediate layer / PO layer. An adhesive layer may be provided between the layers constituting the gas barrier laminate.

  For example, the gas barrier laminate may have the following configuration from the layer that is the outer side of the pouch with a spout toward the layer that is the inner side of the pouch with a spout.

(1) Gas barrier multilayer film / PO layer,
(2) Inorganic vapor deposited film layer / gas barrier multilayer film / PO layer,
(3) Gas barrier multilayer film / inorganic vapor deposition film layer / PO layer,
(4) Gas barrier multilayer film / polyamide layer / PO layer,
(5) Inorganic vapor-deposited film layer / gas barrier multilayer film / polyamide layer / PO layer,
(6) Gas barrier multilayer film / inorganic vapor deposition film layer / polyamide layer / PO layer,
(7) Polyamide layer / gas barrier multilayer film / PO layer,
(8) Polyamide layer / Inorganic vapor deposition film layer / Gas barrier multilayer film / PO layer,
(9) Polyamide layer / Gas barrier multilayer film / Inorganic vapor deposition film layer / PO layer,
(10) Polyamide layer / Gas barrier multilayer film / Polyamide layer / PO layer,
(11) Gas barrier multilayer film / polyester layer / PO layer,
(12) Polyester layer / gas barrier multilayer film / PO layer,
(13) Polyester layer / Gas barrier multilayer film / Polyamide layer / PO layer,
(14) Polyester layer / inorganic vapor deposition film layer / gas barrier multilayer film / PO layer,
(15) Polyester layer / Gas barrier multilayer film / Inorganic vapor deposition film layer / PO layer,
(16) Gas barrier multilayer film / EVOH layer / PO layer,
(17) Gas barrier multilayer film / EVOH layer / polyamide layer / PO layer,
(18) Gas barrier multilayer film / polyamide layer / EVOH layer / PO layer,
(19) Polyamide layer / gas barrier multilayer film / EVOH layer / PO layer.

  An adhesive layer may be provided between the layers constituting these pouches with a spout. Moreover, when the gas barrier layer is laminated | stacked only on the single side | surface of a base material, a gas barrier layer may exist inside a base material and may exist outside a base material. The polyolefin layer, polyamide layer, polyester layer, inorganic vapor deposition film layer, and EVOH layer will be described below.

  As the polyolefin (PO) layer, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-α olefin copolymer, A layer made of at least one resin selected from an ionomer, an ethylene-acrylic acid copolymer, an ethylene-methyl acrylate copolymer, an ethylene-methacrylic acid copolymer, and an ethylene-propylene copolymer may be used. Moreover, you may use the film obtained by extruding the said at least 1 sort (s) of resin. These polyolefin layers may be either stretched or unstretched. The PO layer used in the pouch with a spout of the present invention is made of unstretched low-density polyethylene, unstretched linear (linear) low-density polyethylene, or unstretched polypropylene from the viewpoint of moldability and heat resistance. And is more preferably made of unstretched polypropylene.

  The thickness of the PO layer is not particularly limited, but is preferably in the range of 10 μm to 200 μm, more preferably in the range of 20 μm to 150 μm from the viewpoint of mechanical toughness, impact resistance, puncture resistance, and the like. preferable.

  As the polyamide layer, a film obtained by extruding at least one resin selected from nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, nylon 612, and nylon MXD6 resin can be used. These polyamide layers may be either stretched or unstretched. A preferred polyamide layer includes a film made of nylon 6 or nylon 66 (for example, a uniaxial or biaxially stretched film).

  The thickness of the polyamide layer is not particularly limited, but is preferably in the range of 5 μm to 200 μm, more preferably in the range of 5 μm to 100 μm from the viewpoint of mechanical toughness, impact resistance, puncture resistance, and the like. preferable.

  As the polyester layer, a film obtained by extruding at least one resin selected from polyethylene terephthalate, polyethylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, and polybutylene naphthalate can be used. These polyester layers may be stretched or unstretched. Preferred polyester layers include films made of polyethylene terephthalate or polyethylene naphthalate (for example, uniaxially or biaxially stretched film).

  The thickness of the polyester layer is not particularly limited, but is preferably in the range of 5 μm to 200 μm, more preferably in the range of 5 μm to 100 μm, from the viewpoint of mechanical toughness, impact resistance, puncture resistance, and the like. preferable.

  As said inorganic vapor deposition film layer, the film which vapor-deposited the inorganic layer on a stretched film can be used. As the stretched film, a uniaxially or biaxially stretched polyester film, polyamide film, polyolefin film, or the like can be used. As the inorganic layer, the above-described inorganic layer can be used.

  As the EVOH layer (ethylene-vinyl alcohol copolymer layer), a film obtained by extruding a saponified resin of an ethylene-vinyl acetate copolymer can be used. The EVOH layer may be a uniaxially stretched film, a biaxially stretched film, or an unstretched film, but a biaxially stretched film is preferable. The thickness of the EVOH layer is not particularly limited, but is preferably in the range of 5 μm to 200 μm, and more preferably in the range of 5 μm to 100 μm, from the viewpoints of gas barrier properties, mechanical toughness, workability, and the like.

  The polyolefin layer, polyamide layer, polyester layer, inorganic vapor deposition film layer, and EVOH layer may be bonded to other layers by a known method such as a dry lamination method, a wet lamination method, or a hot melt lamination method. For example, an unstretched polyolefin film, a stretched polyolefin film, an unstretched polyamide film, a stretched polyamide film, and another layer (film) may be bonded together. Further, a PO layer or a polyamide layer may be formed on another layer (film) by a known T-die extrusion method or the like. An adhesive layer may be disposed between the polyolefin layer and other layers. The adhesive layer can be formed using an anchor coating agent, an adhesive, an adhesive resin, or the like.

  The gas barrier laminate may include an unstretched polypropylene layer disposed inside the outermost layer.

[Method for producing gas barrier laminate]
Hereinafter, a method for producing the gas barrier laminate used in the present invention will be described. According to this method, a gas barrier laminate can be easily produced. Since the materials used in the manufacturing method of the present invention and the configuration of the laminate are the same as those described above, description of overlapping portions may be omitted.

  The production method of the present invention includes steps (i) and (ii).

  Step (i) is a step of forming, on a substrate, a layer made of a composition containing a hydrolysis condensate of compound (L) containing a hydrolyzable characteristic group and polymer (X). . The layer is formed directly on the substrate or is formed on the substrate via another layer. Compound (L) includes compound (A) and compound (B). It should be noted that the reactivity of hydrolysis and condensation of the compound (L) can be controlled by adding the compound (D) having a carboxyl group-containing molecular weight of 100 or less to the compound (L). The gas barrier property and hot water resistance of the body are good. Details of the compound (D) will be described later.

  About a compound (A) and a compound (B), and the ratio of those compounds, it is the same as that of what was demonstrated about the composition which comprises a gas barrier layer.

  The next step (ii) is a step of bringing the layer formed in step (i) into contact with a solution containing divalent or higher-valent 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. . By step (ii), at least a part of the —COO— group contained in the functional group (F) of the polymer (X) is neutralized.

Hereinafter, step (i) will be described in detail. In addition, when the compound (L) which is not hydrolytically condensed and a carboxylic acid containing polymer are mixed, both may react and it may become difficult to apply | coat a solution (U). Therefore, step (i)
(Ia) a solution comprising at least one compound selected from the compound (A) and a partial hydrolysis condensate of the compound (A), and a compound (D) containing a carboxyl group and having a molecular weight of 100 or less Preparing (S);
(Ib) preparing a solution (T) by mixing the solution (S) with at least one compound selected from the compound (B) and a partially hydrolyzed condensate of the compound (B);
(Ic) forming a hydrolysis condensate (oligomer (V)) of a plurality of compounds (L) containing the compound (A) and the compound (B) in the solution (T);
(Id) a step of preparing a solution (U) by mixing the solution (T) having undergone the step (ic) and the polymer (X);
(Ie) including a step of forming a layer by applying the solution (U) to a substrate and drying it.

  More specifically, the oligomer (V) obtained by hydrolyzing and condensing the compound (L) includes a compound (L) partially hydrolyzed, a compound (L) completely hydrolyzed, a compound (L ) Is partially hydrolyzed and condensed, and compound (L) is at least one metal element-containing compound selected from completely hydrolyzed and partially condensed. Hereinafter, such a metal element-containing compound may be referred to as “compound (L) -based component”. Hereinafter, the step (ia), the step (ib), the step (ic), the step (id), and the step (ie) will be described more specifically.

  Step (ia) is a step of hydrolyzing and condensing the compound (A) constituting the compound (L) under specific conditions. It is preferable to hydrolyze and condense the compound (A) in a reaction system containing the compound (A), an acid catalyst, water and, if necessary, an organic solvent. Specifically, a technique used in a known sol-gel method can be applied. When hydrolyzing and condensing, it is extremely important to add a compound (D) containing a carboxyl group and having a molecular weight of 100 or less (hereinafter sometimes simply referred to as compound (D)) in order to control the reaction. Preferably, by adding the compound (D), gelation can be suppressed in the step of hydrolyzing and condensing the compound (A).

  Compound (D) is compound (A), compound (A) partially hydrolyzed, compound (A) completely hydrolyzed, compound (A) partially hydrolyzed and condensed, And a metal element-containing compound containing at least one compound selected from those in which the compound (A) is completely hydrolyzed and partially condensed (hereinafter, this metal element-containing compound is referred to as “compound (A) component”). And the compound (D) acts on the compound (A) system component, the above-mentioned effect is exhibited. The method for adding the compound (D) is not particularly limited as long as the compound (A) is added before the component of the compound (A) is gelled by the hydrolysis condensation reaction. be able to. First, compound (D), water, and an organic solvent as necessary are mixed to prepare an aqueous solution of compound (D). Subsequently, an aqueous solution of compound (D) is added to the compound (A) system component, A solution (S) in which the compound (D) acts on the compound (A) component can be obtained. Although there is no restriction | limiting in the usage-amount of the water mixed with a compound (D), From the viewpoint of obtaining a uniform solution (S) with a high concentration, ratio of [number of moles of water] / [number of moles of compound (D)] Is preferably in the range of 25/1 to 300/1, more preferably in the range of 50/1 to 200/1, and even more preferably in the range of 75/1 to 150/1.

  From the viewpoint of improving the reaction control of the compound (A) and the gas barrier property of the gas barrier laminate with respect to the amount of the compound (D) used, [number of moles of the compound (D)] / [number of moles of the compound (A)] ] Is preferably in the range of 0.25 / 1 to 30/1, more preferably in the range of 0.5 / 1 to 20/1, and 0.75 / 1 to 10/1. More preferably, it is in the range.

  The compound (D) is not particularly limited as long as it is a compound containing a carboxyl group and having a molecular weight of 100 or less. From the viewpoint of increasing the reaction rate between the compound (A) and the functional group (F) of the polymer (X) and improving the hot water resistance and gas barrier properties of the gas barrier laminate, acetic acid and propionic acid are used as the compound (D). And hexanoic acid, and acetic acid is most preferred.

  In step (ib), a solution (T) is prepared. Specifically, for example, a solution (S) and an organic solvent as necessary are added to the compound (B) which is a constituent component of the compound (L), and then an acid catalyst, water and an organic solvent as needed are added. The solution (T) can be prepared by the method of adding.

  In the step (ic), hydrolysis and condensation are performed in a reaction system containing, for example, the compound (A) -based component, the compound (B), the acid catalyst, water, and, if necessary, an organic solvent. A technique used in a known sol-gel method can be applied to this technique. Thereby, compound (A) system component, compound (B), compound (B) partially hydrolyzed, compound (B) completely hydrolyzed, compound (B) partially hydrolyzed A solution of the metal element-containing compound containing at least one selected from the condensed product and the compound (B) which is completely hydrolyzed and partially condensed can be obtained.

  By carrying out the reaction in such a step, the generation of gel during the preparation of the oligomer (V) can be prevented, and further the reactivity of the oligomer (V) can be controlled. Therefore, gelatinization at the time of mixing oligomer (V) and polymer (X) can be prevented.

As the acid catalyst used in step (ia) and step (ib), a known acid can be used. For example, hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, benzoic acid, acetic acid, lactic acid, Butyric acid, carbonic acid, oxalic acid, maleic acid and the like can be used. Of these, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, lactic acid and butyric acid are particularly preferred. Preferred amount of acid catalyst may vary depending on the type of acid used, the metal atom to 1 mol of the compound (L), is preferably in the range of 1 × 10 ^-5 to 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. When the amount of the acid catalyst used is within this range, a gas barrier laminate having a high gas barrier property can be obtained.

  Moreover, although the usage-amount of the water used by process (ia) and process (ib) changes with kinds of compound (L), with respect to 1 equivalent of characteristic groups which have the hydrolyzability of compound (L). The range is preferably 0.05 to 10 equivalents, more preferably 0.1 to 5 equivalents, and still more preferably 0.2 to 3 equivalents. When the amount of water used is in this range, the gas barrier property of the resulting gas barrier laminate is particularly excellent. In addition, in the step (ia) and the step (ib), when a component containing water such as hydrochloric acid is used, the amount of water used is also taken into account the amount of water introduced by the component. Is preferably determined.

  Furthermore, in the step (ia) and the step (ib), 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. For example, 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. Specifically, methanol is preferred for tetramethoxysilane and ethanol is preferred for tetraethoxysilane. The amount of the organic solvent to be used is not particularly limited, but it is preferable that the concentration of the compound (L) is 1 to 90% by weight, more preferably 10 to 80% by weight, and still more preferably 10 to 60% by weight. .

  In step (ia), step (ib), and step (ic), the temperature of the reaction system is necessarily limited when the compound (L) is hydrolyzed or condensed in the reaction system. However, it is usually in the range of 2 to 100 ° C, preferably in the range of 4 to 60 ° C, and more preferably in the range of 6 to 50 ° C. The reaction time varies depending on the reaction conditions such as the amount and type of the acid catalyst, but is usually in the range of 0.01 to 60 hours, preferably in the range of 0.1 to 12 hours, more preferably 0.8. The range is 1 to 6 hours. The reaction can be performed in an atmosphere of various gases such as air, carbon dioxide, nitrogen, and argon.

  In the step (id), the solution (T) containing the oligomer (V) obtained in the step (ic) and the carboxylic acid-containing polymer (= polymer (X)) are mixed to form a solution (U ). The solution (U) can be prepared using the solution (T), the carboxylic acid-containing polymer, and, if necessary, water and an organic solvent. For example, a method of adding and mixing the solution (T) to a solution in which the carboxylic acid-containing polymer is dissolved can be employed. Moreover, the method of adding and mixing the solution which dissolved the carboxylic acid containing polymer in water or the organic solvent to the solution (T) is also employable. In any method, the solution (T) to be added or the solution in which the carboxylic acid-containing polymer is dissolved may be added at once, or may be added in divided portions.

  The solution in which the carboxylic acid-containing polymer in step (id) is dissolved can be prepared by the following method. What is necessary is just to select the solvent to be used according to the kind of carboxylic acid containing polymer. For example, in the case of a water-soluble polymer such as polyacrylic acid or polymethacrylic acid, water is suitable. In the case of a polymer such as an isobutylene-maleic anhydride copolymer or a styrene-maleic anhydride copolymer, water containing an alkaline substance such as ammonia, sodium hydroxide, or potassium hydroxide is preferred. In addition, alcohols such as methanol and ethanol; ethers such as tetrahydrofuran, dioxane and trioxane; ketones such as acetone and methyl ethyl ketone; glycols such as ethylene glycol and propylene glycol, as long as the dissolution of the carboxylic acid-containing polymer is not hindered Glycol derivatives such as methyl cellosolve, ethyl cellosolve, n-butyl cellosolve; glycerin; acetonitrile, dimethylformamide, dimethyl sulfoxide, sulfolane, dimethoxyethane and the like can be used in combination.

  In the carboxylic acid-containing polymer contained in the solution (U), a part of the —COO— group (eg, 0.1 to 10 mol%) contained in the functional group (F) is neutralized by monovalent ions. May be. The degree of neutralization of the functional group (F) by monovalent ions is more preferably in the range of 0.5 to 5 mol% from the viewpoint of improving the transparency of the resulting gas barrier laminate. More preferably, it is in the range of ˜3 mol%. Examples of 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 base material. 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.

  From the viewpoint of the storage stability of the solution (U) and the gas barrier properties of the resulting gas barrier laminate, the pH of the solution (U) is preferably in the range of 1.0 to 7.0, 1.0 to 6 More preferably, it is in the range of 0.0, and more preferably in the range of 1.5 to 4.0.

  The pH of the solution (U) can be adjusted by a known method, for example, acidic compounds such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, butyric acid, ammonium sulfate, sodium hydroxide, potassium hydroxide, ammonia, trimethylamine, pyridine, It can adjust by adding basic compounds, such as sodium carbonate and sodium acetate. At this time, if a basic compound that provides a monovalent cation is used in the solution, a part of the carboxyl group and / or carboxylic anhydride group of the carboxylic acid-containing polymer may be neutralized with a monovalent ion. The effect that it can be obtained.

The step (ie) will be described. The state of the solution (U) prepared in the step (id) 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). 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. When the viscosity of the solution (U) is in the above range, the storage stability is excellent and the gas barrier property of the obtained gas barrier laminate is often improved.

  In order to adjust the viscosity of the solution (U) to be within the above range, for example, adjusting the concentration of solids, 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.

  In addition, in order to facilitate the application of the solution (U) to the base material, 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. Examples of 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 and the like.

  In addition, the solution (U) may be carbonate, hydrochloride, nitrate, hydrogen carbonate, sulfate, hydrogen sulfate, phosphate, borate, alumina as long as it does not impair the effects of the present invention. Inorganic acid metal salts such as acid salts; organic acid metal salts such as oxalate, acetate, tartrate and stearate; acetylacetonate metal complexes such as aluminum acetylacetonate; cyclopentadiene such as titanocene Metal complexes such as enyl metal complexes and cyano metal complexes; layered clay compounds, crosslinking agents, compounds containing two or more amino groups as described above (P), compounds containing two or more hydroxyl groups as described above (Q), and other It may contain a polymer compound, a plasticizer, an antioxidant, an ultraviolet absorber, a flame retardant and the like. The solution (U) may contain fine metal oxide powder or fine silica powder.

  The solution (U) prepared in the step (id) is applied to at least one surface of the substrate in the step (ie). Before applying the solution (U), 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.

  After the solution (U) is applied on the substrate in the step (ie), 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. A drying temperature will not be restrict | limited especially if it is 15-20 degreeC or more lower than the flow start temperature of a base material, and 15-20 degreeC or more lower than the thermal decomposition start temperature of a 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.

  In the gas barrier laminate used in the present invention, 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 for the solution (U), the drying speed of the solution (U) after the solution (U) is applied to the substrate, and the like. For example, when the contact angle of water with respect to the gas barrier layer surface is measured and the contact angle is smaller than the above-described predetermined range, the reaction time of the step (ia) and the step (ic) is increased. It is possible to increase the contact angle (that is, to form an appropriate skin layer). On the other hand, when the contact angle is larger than the predetermined range, it is possible to reduce the contact angle by shortening the reaction time of the step (ia) and the step (ic).

  By bringing the laminate (I) obtained by the above step into contact with a solution containing metal ions having a valence of 2 or more (hereinafter sometimes referred to as “solution (IW)”) by the step (ii) (ionization step). A gas barrier laminate (laminate (II)) is obtained. The ionization process may be performed at any stage as long as the effects of the present invention are not impaired. For example, 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 that releases a divalent or higher valent metal ion (polyvalent metal compound) upon dissolution. As 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. Examples of such organic solvents 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.

As the polyvalent metal compound, compounds capable of releasing the metal ions exemplified for the gas barrier laminate used in the present invention (that is, divalent or higher metal ions) can be used. For example, calcium acetate, calcium hydroxide, barium hydroxide, calcium chloride, calcium nitrate, calcium carbonate, magnesium acetate, magnesium hydroxide, magnesium chloride, magnesium carbonate, iron (II) acetate, iron (II) chloride, iron acetate ( III), iron chloride (III), zinc acetate, zinc chloride, copper acetate (II), copper acetate (III), lead acetate, mercury acetate (II), barium acetate, zirconium acetate, barium chloride, barium sulfate, nickel sulfate Lead sulfate, zirconium chloride, zirconium nitrate, aluminum sulfate, potassium alum (KAl (SO ₄ ) ₂ ), titanium (IV) sulfate, and the like can be used. 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 to 20% by weight.

  When the laminate (I) is brought into contact with the solution (IW), 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.

  It is desirable to remove the solvent remaining in the laminate after contacting the laminate (I) with the solution (IW). The method for removing the solvent is not particularly limited, and a known method can be applied. Specifically, drying methods such as a hot air drying method, a hot roll contact method, an infrared heating method, and a microwave heating method can be applied singly or in combination of two or more. The temperature at which the solvent is removed is not particularly limited as long as it is 15 to 20 ° C. or more lower than the flow start temperature of the substrate and 15 to 20 ° C. or lower than the thermal decomposition start temperature of the carboxylic acid-containing polymer. The drying temperature is preferably in the range of 40 to 200 ° C, more preferably in the range of 60 to 150 ° C, and still more preferably in the range of 80 to 130 ° C. The removal of the solvent may be carried out under normal pressure or reduced pressure.

  In order not to impair the appearance of the surface of the gas barrier laminate, it is preferable to remove excess polyvalent metal compound adhering to the surface of the laminate before or after removing the solvent. As a method for removing the polyvalent metal compound, washing using a solvent in which the polyvalent metal compound dissolves is preferable. As the solvent in which the polyvalent metal compound dissolves, a solvent that can be used for the solution (IW) can be used, and the same solvent as the solvent for the solution (IW) is preferably used.

  The production method of the present invention further includes a step of heat-treating the layer formed in step (i) at a temperature of 120 to 240 ° C. after step (i) and before and / or after step (ii). But you can. That is, you may heat-process with respect to laminated body (I) or (II). The heat treatment may be performed at any stage as long as the removal of the solvent of the coated solution (U) is almost completed, but the layered product (that is, the layered product (I)) before the ionization step is performed. By performing the heat treatment, a gas barrier laminate having a good surface appearance can be obtained. The temperature of the heat treatment is preferably in the range of 120 ° C to 240 ° C, more preferably in the range of 140 to 240 ° C, and still more preferably in the range of 160 ° C to 220 ° C. The heat treatment can be performed in air, under a nitrogen atmosphere, under an argon atmosphere, or the like.

  In the production method of the present invention, 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. Further, instead of ultraviolet irradiation, radiation such as an electron beam or γ-ray may be irradiated.

  Only one of heat treatment and ultraviolet irradiation may be performed, or both may be used in combination. By performing heat treatment and / or ultraviolet irradiation, the gas barrier performance of the laminate may be expressed to a higher degree.

  In order to dispose the adhesive layer (H) between the base material and the gas barrier layer, a treatment (treatment with an anchor coating agent or application of an adhesive) is performed on the surface of the base material before application of the solution (U). You may give it. In that case, after the step (i) (application of the solution (U)) and before the heat treatment and the step (ii) (ionization step), 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 still more preferably in the range of 1 to 5 days. By performing such an aging treatment, the adhesive force between the base material and the gas barrier layer becomes stronger. After the aging treatment, it is preferable to perform the above heat treatment (heat treatment at 120 ° C. to 240 ° C.).

[Spout]
Hereinafter, the spout used in the present invention will be described.

  The spout in the pouch with a spout of the present invention can be formed by injection molding of polyethylene, polystyrene, polypropylene or the like. Usually, a spout is arrange | positioned between two gas barrier laminated bodies in the peripheral part of the gas barrier laminated body which comprises a pouch, and is mounted | worn to a pouch in the state melt | fused to them. Therefore, the spout is usually formed of a material that can be fused to the inner layer of the gas barrier laminate constituting the pouch.

[Manufacturing method of pouch with spout]
The pouch with a spout of the present invention can be produced by a general bag making method. The pouch can be formed in a shape and size according to the purpose of use. As a bag making method, a method of bag making by forming a gas barrier laminate can be adopted. When bag making is performed from a laminated body, the laminated body is overlapped, and the surroundings are heat-sealed to form a bag, and then a spout (plug member) may be attached by heat sealing.

  There is no restriction | limiting in particular about the magnitude | size of the pouch with a spout of this invention, The quantity of the content may be 100 mL-2000 mL. In the pouch with a spout of the present invention, a spout can be provided at an arbitrary position. For example, the spout may be provided at the upper center or upper corner of the pouch.

  There is no restriction | limiting in particular in the method of filling the content in the pouch with a spout of this invention. For example, the content may be filled from a spout mouth, from the top of the pouch, or from the bottom of the pouch. When filling the contents from the top or bottom of the pouch, the pouch is heat sealed after filling.

  The pouch with a spout of the present invention has transparency and flexibility and can be retorted under severe conditions. The pouch of the present invention can be used as a container for liquid drinks (for example, soft drinks), jelly drinks, yogurts, fruit sauces, seasonings, functional water, and liquid foods. In addition, the pouch of the present invention exhibits high oxygen barrier properties not only before retorting but also after retorting. Therefore, the pouch of the present invention can be preferably used as a container for liquid pharmaceuticals such as amino acid infusions, electrolyte infusions, saccharide infusions, and fat emulsions for infusion.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the following examples, when describing the layer structure of the laminate, only the substance name may be described, and the “layer” may be omitted.

[Production and evaluation of gas barrier laminate and laminate]
The gas barrier laminate and laminate described below were prepared and evaluated. Evaluation was performed by the following methods (1) to (9).

(1) 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 oxygen permeability (unit: cc / m ² / day / atm) was measured under the conditions of a temperature of 20 ° C., an oxygen pressure of 1 atm, and a carrier gas pressure of 1 atm (cc = cm ³ ). Nitrogen gas containing 2% by volume of hydrogen gas was used as the carrier gas. At this time, the humidity was set to 85% RH, and the oxygen supply side and the carrier gas side were set to the same humidity. For the laminate in which the gas barrier layer was formed only on one side of the substrate, the laminate was set so that the gas barrier layer was directed to the oxygen supply side and the substrate was directed to the carrier gas side.

(2) Oxygen barrier property after 10% elongation and before retort treatment First, the laminate was cut into 30 cm × 21 cm. Next, the cut-out laminate was stretched by 10% using a manual stretching device under the conditions of 23 ° C. and 50% RH, and held for 5 minutes in the stretched state. Thereafter, the oxygen permeability was measured by the same method as described above.

(3) Contact angle The laminate was conditioned for 24 hours under conditions of a temperature of 20 ° C and a humidity of 65% RH. Thereafter, 2 μL of water was dropped onto the gas barrier layer using an automatic contact angle meter (manufactured by Kyowa Interface Science, DM500) under conditions of a temperature of 20 ° C. and a humidity of 65% RH. And the contact angle of a gas barrier layer and water was measured by the method based on Japanese Industrial Standard (JIS) -R3257.

(4) Tensile strength and elongation, Young's modulus 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. About the cut-out laminated body, tensile strength and Young's modulus were measured by the method based on JIS-K7127 on the conditions of temperature 23 degreeC and humidity 50% RH.

(5) Dry heat shrinkage The laminate was cut into 10 cm × 10 cm, and the length in MD and TD was measured with calipers. This laminate was heated in a dryer at 80 ° C. for 5 minutes, and the length in MD and TD after heating was measured. And the dry heat shrinkage rate was measured from the following formula.
Dry heat shrinkage (%) = (l _b −l _a ) × 100 / l _b
[Wherein _lb represents a length before heating. l _a represents the length after heating. ]

(6) Degree of neutralization of carboxyl groups by metal ions (degree of ionization)
[Calculation of ionization degree by FT-IR]
Polyacrylic acid having a number average molecular weight of 150,000 was dissolved in distilled water, and the carboxyl group was neutralized with a predetermined amount of sodium hydroxide. The obtained aqueous solution of neutralized polyacrylic acid was coated on a substrate so as to have the same thickness as the gas barrier layer of the laminate to be measured for ionization degree, and dried. 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 polyamide film (manufactured by Unitika Ltd., Emblem ON-BC (trade name), thickness 15 μm, hereinafter sometimes abbreviated as “OPA”) was used. In this way, a standard sample [laminated body (layer made of neutralized polyacrylic acid / AC / OPA)] having a carboxyl group neutralization degree of 0, 25, 50, 75, 80, and 90 mol% was prepared. Produced. About these samples, 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 1600cm ^-1 ~1850cm ^-1 and 1500cm ^-1 ~1600cm ^- The ratio of the maximum absorbance was calculated for the peak observed in the range of ¹ . And the calibration curve 1 was created using the calculated ratio and the ionization degree of each standard sample.

A laminate using a stretched polyamide film (OPA) as a base material is included in the gas barrier layer in a mode of ATR (total reflection measurement) using a Fourier transform infrared spectrophotometer (manufactured by Perkin Elmer, Spectrum One). The peak of C = O stretching vibration was observed. Peak attributed to C = O stretching vibration of the carboxyl group of the ionization front of a carboxylic acid-containing polymer, was observed in the range of 1600cm ^-1 ~1850cm ^-1. Furthermore, C = O stretching vibration of the carboxyl group after being ionized was observed in the range of 1500cm ^-1 ~1600cm ^-1. Then, the ratio was calculated from the maximum absorbance in each range, and the degree of ionization was determined using the ratio and the calibration curve 1.

[Calculation of ionization degree by fluorescent X-ray]
About the laminated body using OPA mentioned above as a base material, the standard sample from which the degree of ionization differs was measured from the measurement of FT-IR. Specifically, eleven types of standard samples having different degrees of ionization (ions: calcium ions) of about 10 mol% between 0 to 100 mol% were prepared. For each sample, the fluorescence X-ray intensity of calcium element was measured using a wavelength dispersion type fluorescent X-ray apparatus (manufactured by Rigaku Corporation, ZSXmini II), and a calibration curve 2 was created from the degree of ionization measured in advance by FT-IR. did. Using the obtained calibration curve 2, the degree of calcium ionization of the laminate produced under various conditions was calculated.

  Also in the case of ionization with other metal ions (magnesium ion, zinc ion, etc.), the calibration curve 2 was created by the same method as described above, and the degree of ionization was calculated.

  For a laminate (such as PET) using a substrate other than OPA, the degree of ionization was calculated using the calibration curve 2 obtained by fluorescent X-ray intensity measurement.

(7) Weight of hydrolysis condensate and polymer (X) By the method described above, the weight of the inorganic component derived from compound (L) and the weight of the organic component derived from compound (L) and polymer (X ) And the total weight of the organic components derived from it were calculated.

(8) Oxygen barrier property after retorting Two laminates (size: 12 cm × 12 cm) were produced. Then, the two sheets were laminated so that the unstretched polypropylene film (Tosero Co., Ltd., RXC-18 (trade name), thickness 50 μm, hereinafter abbreviated as “CPP”) might be inside. The three sides of the laminate were heat sealed to 5 mm from the end. After injecting 80 g of distilled water between the two heat-sealed laminates, the remaining fourth side was similarly heat-sealed. In this way, a pouch containing distilled water was produced.

  Next, the pouch was put into a retort treatment device (manufactured by Nisaka Seisakusho, Flavor Ace RCS-60), and retort treatment was performed under the conditions of 120 ° C., 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. Thereafter, 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.

(9) Appearance after retort treatment First, a pouch similar to the pouch used in the measurement of oxygen barrier properties after retort treatment was produced. This pouch was retorted at 135 ° C., 60 minutes, and 0.25 MPa. After the retort treatment, the heating was stopped, and when the internal temperature reached 60 ° C., the pouch was taken out from the retort treatment apparatus and left in a room at 20 ° C. and 65% RH for 1 hour. Then, the appearance is observed. When there is no cloudiness as before the retort, it is “very good (◎)”. When there is a slight cloudiness but there is no practical problem, it is “good (○)”. When it was cloudy, it was determined as “bad (×)”.

<Laminated body (1)>
Polyacrylic acid (PAA) having a number average molecular weight of 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. Subsequently, 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.

  Further, 60 parts by weight of acetic acid and 1800 parts by weight of distilled water were mixed, and 204 parts by weight of aluminum isopropoxide (AIP) (AIP / acetic acid / distilled water = 1/1/100 (molar ratio)) was stirred into this acetic acid aqueous solution. And then heated at 80 ° C. for 1 hour to obtain an AIP aqueous solution (S1) having a concentration of 9.88% by weight.

  Subsequently, the molar ratio of Al / Si was 1.2 / 98.8, and the weight ratio of [inorganic component derived from tetramethoxysilane (TMOS) and AIP] / [partially neutralized product of PAA] was 40.2 / A mixed solution (U1) was prepared so as to be 59.8. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 8.5 parts by weight of the above 9.88% by weight AIP aqueous solution (S1) was added thereto. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS would be 1.95 molar equivalents, and hydrolysis and condensation reactions were carried out at 10 ° C. for 1 hour. And a mixed solution (T1) was obtained. Subsequently, after diluting the mixed solution (T1) with 425 parts by weight of distilled water and 222 parts by weight of methanol, 228 parts by weight of an aqueous solution of a partially neutralized product of PAA (concentration 13% by weight) was rapidly added while stirring. As a result, a mixed solution (U1) having a solid content concentration of 5% by weight was obtained.

  On the other hand, 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 μm, hereinafter sometimes abbreviated as “PET”), and dried to form a base having an anchor coat layer. A material (AC (0.1 μm) / PET (12 μm)) was prepared. The mixed solution (U1) was coated on the anchor coat layer of the base material by a bar coater so that the thickness after drying was 0.4 μm, and dried at 120 ° C. for 5 minutes. Subsequently, coating was also performed on the opposite surface of the substrate in the same procedure. The obtained laminate was aged at 40 ° C. for 3 days. Next, the laminate was heat-treated at 180 ° C. for 5 minutes using a dryer. Next, the laminate was immersed in a 2% by weight calcium acetate aqueous solution (85 ° C.) for 12 seconds, and then dried at 110 ° C. for 1 minute. In this way, a laminate (1) having a structure of gas barrier layer (0.4 μm) / AC (0.1 μm) / PET (12 μm) / AC (0.1 μm) / gas barrier layer (0.4 μm) is obtained. It was.

<Laminated body (2)>
A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in the laminate (1). The molar ratio of Al / Si is 30.1 / 69.9, and the weight ratio of [inorganic component derived from TMOS and AIP] / [partially neutralized product of PAA] is 25.5 / 74.5. A mixed solution (U2) was prepared. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 293 parts by weight of a 9.88% by weight AIP aqueous solution (S2) was added thereto. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalent, and hydrolysis and condensation reaction was performed at 10 ° C. for 1 hour. And a liquid mixture (T2) was obtained. Subsequently, after diluting the obtained mixed liquid (T2) with 850 parts by weight of distilled water and 405 parts by weight of methanol, 607 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight) was rapidly added while stirring. As a result, a mixed solution (U2) having a solid content concentration of 5% by weight was obtained.

  Using the mixed solution (U2), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (2).

<Laminated body (3)>
A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in the laminate (1). And only the reaction time was changed and the liquid mixture (U3) was prepared.

  Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 8.5 parts by weight of a 9.88% by weight AIP aqueous solution (S3) was added thereto. 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 equivalents, and hydrolysis and condensation reactions were carried out at 10 ° C. for 5 hours. And a liquid mixture (T3) was obtained. Subsequently, after the mixture (T3) was diluted with 425 parts by weight of distilled water and 222 parts by weight of methanol, 228 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight) was rapidly added while stirring. A liquid mixture (U3) having a solid content concentration of 5% by weight was obtained. Using the mixed solution (U3), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (3).

<Laminated body (4)>
AIP was changed to titanium tetraisopropoxide (TIP) to prepare a mixed solution (U4). Specifically, 1200 parts by weight of acetic acid and 1800 parts by weight of distilled water were mixed, and 284 parts by weight of TIP (TIP / acetic acid / distilled water = 1/20/100 (molar ratio)) was added to this aqueous acetic acid solution with stirring. Then, a TIP aqueous solution (S4) having a concentration of 8.6% by weight was obtained by heating at 80 ° C. for 1 hour. Subsequently, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 13.5 parts by weight of TIP aqueous solution (S4) was added thereto. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalent, and hydrolysis and condensation reaction was performed at 10 ° C. for 5 hours. And a liquid mixture (T4) was obtained. Then, the liquid mixture (U4) with a solid content concentration of 5 weight% was obtained with the composition and method similar to the laminated body (1).

  Using the mixed solution (U4), coating, heat treatment, ionization, and drying were performed in the same manner as in the laminate (1) to obtain a laminate (4).

<Laminated body (5)>
AIP was changed to zirconium tetraisopropoxide (ZIP) to prepare a mixed solution (U5). Specifically, 1200 parts by weight of acetic acid and 1800 parts by weight of distilled water were mixed, and 327 parts by weight of ZIP (ZIP / acetic acid / distilled water = 1/20/100 (molar ratio)) was added to this aqueous acetic acid solution with stirring. Thereafter, the mixture was heated at 80 ° C. for 1 hour to obtain a 9.8 wt% aqueous ZIP solution (S5). Next, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 13.6 parts by weight of the 9.8% by weight ZIP aqueous solution (S5) was added thereto. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalent, and hydrolysis and condensation reaction was performed at 10 ° C. for 5 hours. And a liquid mixture (T5) was obtained. Subsequently, a mixed liquid (U5) having a solid content concentration of 5% by weight was obtained by the same composition and method as those of the laminate (1).

  Using the mixed solution (U5), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (5).

<Laminated body (6)>
A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in the laminate (1). And with the same charging ratio as the laminate (3) except that the weight ratio of [inorganic component derived from TMOS and AIP] / [partially neutralized product of PAA] was 30.2 / 69.8, A mixed solution (U6) was prepared. Specifically, first, a mixed solution (T6) was prepared by the same composition and method as the mixed solution (T3) obtained from the laminate (3). After diluting this mixed solution (T6) 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. A liquid mixture (U6) having a concentration of 5% by weight was obtained.

  Using the mixed solution (U6), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (6).

<Laminated body (7)>
A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in the laminate (1). And the liquid mixture (U7) was prepared by the preparation ratio similar to a laminated body (6) except having made it the molar ratio of Al / Si becoming 1.9 / 98.1. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 13.2 parts by weight of the 9.88 wt% AIP aqueous solution (S7) was added thereto. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalent, and hydrolysis and condensation reaction was performed at 10 ° C. for 5 hours. And a liquid mixture (T7) was obtained. Then, the liquid mixture (U7) whose solid content concentration is 5 weight% with the composition and method similar to a laminated body (6) was obtained.

  Using the mixed solution (U7), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (7).

<Laminated body (8)>
A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in the laminate (1). And the liquid mixture (U8) was prepared by the preparation ratio similar to a laminated body (6) except having made it the molar ratio of Al / Si becoming 2.8 / 97.2. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 19.8 parts by weight of the 9.88 wt% AIP aqueous solution (S8) was added thereto. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalent, and hydrolysis and condensation reaction was performed at 10 ° C. for 5 hours. And a liquid mixture (T8) was obtained. Then, the liquid mixture (U8) whose solid content concentration is 5 weight% with the composition and method similar to a laminated body (6) was obtained.

  Using the mixed solution (U8), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (8).

<Laminated body (9)>
A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in the laminate (1). The same charging ratio as that of the laminate (2), that is, the molar ratio of Al / Si was 30/70, and the weight ratio of [inorganic component derived from TMOS and AIP] / [partially neutralized product of PAA] was 25.5. A mixed solution (U9) was prepared so as to be /74.5. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 293 parts by weight of a 9.88 wt% AIP aqueous solution (S9) was added thereto. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalent, and hydrolysis and condensation reaction was performed at 10 ° C. for 5 hours. And a liquid mixture (T9) was obtained. Subsequently, after diluting the obtained mixed liquid (T9) with 850 parts by weight of distilled water and 405 parts by weight of methanol, 607 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight) was rapidly added while stirring. As a result, a mixed solution (U9) having a solid content concentration of 5% by weight was obtained.

  Using the mixed solution (U9), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (9).

<Laminated body (10)>
A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in the laminate (1). The molar ratio of Al / Si is 0.1 / 99.9, and the weight ratio of [inorganic component derived from TMOS and AIP] / [partially neutralized product of PAA] is 80.0 / 20.0. A mixed solution (U10) was prepared. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 0.7 part by weight of a 9.88 wt% AIP aqueous solution (S10) was added thereto. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalent, and hydrolysis and condensation reaction was performed at 10 ° C. for 5 hours. And a liquid mixture (T10) was obtained. Subsequently, after the mixed liquid (T10) was diluted with 212 parts by weight of distilled water and 131 parts by weight of methanol, 38 parts by weight of an aqueous solution of PAA partially neutralized (concentration 13% by weight) was rapidly added while stirring. A mixed solution (U10) having a solid content concentration of 5% by weight was obtained.

  Using the mixed solution (U10), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (10).

<Laminated body (11)>
A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in the laminate (1). The molar ratio of Al / Si is 29.9 / 70.1, and the weight ratio of [inorganic component derived from TMOS and AIP] / [partially neutralized product of PAA] is 36.9 / 63.1. A mixed solution (U11) was prepared. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 290 parts by weight of a 9.88 wt% AIP aqueous solution (S11) was added thereto. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalent, and hydrolysis and condensation reaction was performed at 10 ° C. for 5 hours. And a liquid mixture (T11) was obtained. Subsequently, after the mixture (T11) 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. A liquid mixture (U11) having a solid content concentration of 5% by weight was obtained.

  Using the mixed solution (U11), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (11).

<Laminated body (12)>
A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in the laminate (1). The molar ratio of Al / Si is 0.1 / 99.9, and the weight ratio of [inorganic component derived from TMOS and AIP] / [partially neutralized product of PAA] is 70.0 / 30.0. A mixed solution (U12) was prepared. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 0.7 part by weight of a 9.88 wt% AIP aqueous solution (S12) was added thereto. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalent, and hydrolysis and condensation reaction was performed at 10 ° C. for 5 hours. And a liquid mixture (T12) was obtained. Subsequently, after the mixture (T12) was diluted with 243 parts by weight of distilled water and 144 parts by weight of methanol, 65 parts by weight of an aqueous solution (partial concentration 13% by weight) of a partially neutralized product of PAA was rapidly added while stirring. A mixed solution (U12) having a solid content concentration of 5% by weight was obtained.

  Using the mixed solution (U12), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (12).

<Laminated body (13)>
A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in the laminate (1). The molar ratio of Al / Si is 3.0 / 97.0, and the weight ratio of [inorganic component derived from TMOS and AIP] / [partially neutralized product of PAA] is 20.0 / 80.0. A mixed solution (U13) was prepared. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 20.8 parts by weight of a 9.88 wt% AIP aqueous solution (S13) was added thereto. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalent, and hydrolysis and condensation reaction was performed at 10 ° C. for 5 hours. And a liquid mixture (T13) was obtained. Subsequently, after the mixture (T13) was diluted with 868 parts by weight of distilled water and 412 parts by weight of methanol, 623 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight) was rapidly added while stirring. A liquid mixture (U13) having a solid content concentration of 5% by weight was obtained.

  Using the mixed solution (U13), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (13).

<Laminated body (14)>
A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in the laminate (1). The molar ratio of Al / Si is 3.0 / 97.0 and the weight ratio of [inorganic component derived from TMOS and AIP] / [partially neutralized product of PAA] is 80.0 / 20.0. A mixed solution (U14) was prepared. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 21.0 parts by weight of a 9.88 wt% AIP aqueous solution (S14) was added thereto. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalent, and hydrolysis and condensation reaction was performed at 10 ° C. for 5 hours. And a liquid mixture (T14) was obtained. Subsequently, after the mixture (T14) was diluted with 214 parts by weight of distilled water and 132 parts by weight of methanol, 39 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight) was rapidly added while stirring. A liquid mixture (U14) having a solid content concentration of 5% by weight was obtained.

  Using the mixed solution (U14), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (14).

<Laminated body (15)>
A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in the laminate (1). The molar ratio of Al / Si is 3.0 / 97.0, and the weight ratio of [inorganic component derived from TMOS and AIP] / [partially neutralized product of PAA] is 70.0 / 30.0. A mixed solution (U15) was prepared. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 21.1 parts by weight of a 9.88 wt% AIP aqueous solution (S15) was added thereto. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalent, and hydrolysis and condensation reaction was performed at 10 ° C. for 5 hours. And a liquid mixture (T15) was obtained. Subsequently, after diluting the mixed solution (T15) with 245 parts by weight of distilled water and 145 parts by weight of methanol, 67 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight) was rapidly added while stirring. A liquid mixture (U15) having a solid content concentration of 5% by weight was obtained.

  Using the mixed solution (U15), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (15).

<Laminated body (16)>
A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in the laminate (1). The molar ratio of Al / Si is 2.9 / 97.1, and the weight ratio of [inorganic component derived from TMOS and AIP] / [partially neutralized product of PAA] is 10.2 / 89.8. A mixed solution (U16) was prepared. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 20.3 parts by weight of a 9.88 wt% AIP aqueous solution (S16) was added thereto. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalent, and hydrolysis and condensation reaction was performed at 10 ° C. for 5 hours. And a liquid mixture (T16) was obtained. Subsequently, after the mixture (T16) was diluted with 1700 parts by weight of distilled water and 769 parts by weight of methanol, 1366 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight) was rapidly added while stirring. A liquid mixture (U13) having a solid content concentration of 5% by weight was obtained.

  Using the mixed solution (U16), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (16).

<Laminated body (17)>
A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in the laminate (1). The molar ratio of Al / Si is 3.0 / 97.0, and the weight ratio of [inorganic component derived from TMOS and AIP] / [partially neutralized product of PAA] is 90.2 / 9.8. A mixed solution (U17) was prepared. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 21.3 parts by weight of a 9.88 wt% AIP aqueous solution (S17) was added thereto. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalent, and hydrolysis and condensation reaction was performed at 10 ° C. for 5 hours. And a liquid mixture (T17) was obtained. Subsequently, after the mixed solution (T17) was diluted with 189 parts by weight of distilled water and 121 parts by weight of methanol, 17 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight) was rapidly added while stirring. A liquid mixture (U17) having a solid content concentration of 5% by weight was obtained.

  Using the mixed solution (U17), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (17).

<Laminated body (18)>
A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in the laminate (1). Subsequently, the molar ratio of TMOS / γ-glycidoxydoxypropyltrimethoxysilane (GPTMOS) was 99.5 / 0.5, the molar ratio of Al / Si was 2.8 / 97.2, [TMOS, AIP and A mixed solution (U18) was prepared so that the weight ratio of [inorganic component derived from GPTMOS] / [partially neutralized product of organic component of GPTMOS and PAA] was 30.5 / 69.5. Specifically, first, 49.6 parts by weight of TMOS and 0.4 part by weight of GPTMOS were dissolved in 50 parts by weight of methanol, and a 9.88 wt% AIP aqueous solution (S18) prepared by the same method as that for the laminate (1) was added thereto. 19.6 parts by weight) was added. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to the total of TMOS and GPTMOS was 1.95 molar equivalent, and the mixture was hydrolyzed at 10 ° C. for 5 hours. Decomposition | disassembly and condensation reaction were performed and the liquid mixture (T18) was obtained. Subsequently, after the mixed liquid (T18) was diluted with 566 parts by weight of distilled water and 283 parts by weight of methanol, 352 parts by weight of an aqueous solution of a partially neutralized product of PAA (concentration 13% by weight) was rapidly added while stirring. As a result, a mixed solution (U18) having a solid content concentration of 5% by weight was obtained.

  Using the mixed solution (U18), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (18).

<Laminated body (19)>
A mixed liquid (U19) was obtained with the same charging ratio as that of the laminate (18) except that the molar ratio of TMOS / GPTMOS was 80.0 / 20.0. Specifically, first, 36.0 parts by weight of TMOS and 14.0 parts by weight of GPTMOS were dissolved in 50 parts by weight of methanol, and 19.8 parts by weight of a 9.88% by weight AIP aqueous solution (S19) was added thereto. Further, 3.0 parts by weight of distilled water and 7.4 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to the total of TMOS and GPTMOS was 1.95 molar equivalents, and water was added at 10 ° C. for 5 hours. Decomposition and condensation reaction were performed to obtain a mixed solution (T19). Subsequently, after the mixed liquid (T19) was diluted with 520 parts by weight of distilled water and 302 parts by weight of methanol, 267 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight) was rapidly added while stirring. A liquid mixture (U19) having a solid content concentration of 5% by weight was obtained.

  Using the mixed solution (U19), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (19).

<Laminated body (20)>
A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in the laminate (1). Subsequently, the molar ratio of TMOS / GPTMOS is 89.9 / 10.1, the molar ratio of Al / Si is 3.1 / 96.9, [inorganic components derived from TMOS, AIP and GPTMOS] / [organic of GPTMOS] The mixed solution (U20) was prepared so that the weight ratio of the component and the partially neutralized product of PAA was 31.5 / 68.5. 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, and 20.6 parts by weight of a 9.88% by weight AIP aqueous solution (S20) was added thereto. Further, 3.2 parts by weight of distilled water and 7.8 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to the total of TMOS and GPTMOS was 1.95 molar equivalents, and water was added at 10 ° C. for 5 hours. Decomposition | disassembly and condensation reaction were performed and the liquid mixture (T20) was obtained. Subsequently, after diluting the mixed liquid (T20) with 542 parts by weight of distilled water and 302 parts by weight of methanol, 293 parts by weight of an aqueous solution of a partially neutralized product of PAA (concentration 13% by weight) was rapidly added while stirring. A mixed liquid (U20) having a solid content concentration of 5% by weight was obtained.

  Using the mixed solution (U20), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (20).

<Laminated body (21)>
A mixed liquid (U21) was obtained with the same charging ratio as that of the laminate (18) except that the molar ratio of TMOS to GPTMOS was 98.0 / 2.0. Specifically, first, 48.5 parts by weight of TMOS and 1.5 parts by weight of GPTMOS were dissolved in 50 parts by weight of methanol, and 19.2 parts by weight of a 9.88% by weight AIP aqueous solution (S21) was added thereto. Further, 3.3 parts by weight of distilled water and 8.1 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to the total of TMOS and GPTMOS was 1.95 molar equivalent, and the mixture was hydrolyzed at 10 ° C. for 5 hours. Decomposition and condensation reaction were performed to obtain a mixed solution (T21). Subsequently, after the mixed liquid (T21) was diluted with 562 parts by weight of distilled water and 285 parts by weight of methanol, 345 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight) was rapidly added while stirring. A liquid mixture (U21) having a solid content concentration of 5% by weight was obtained.

  Using the mixed solution (U21), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (21).

<Laminated body (22)>
A mixed liquid (U22) was obtained with the same charging ratio as that of the laminate (18) except that the molar ratio of TMOS / GPTMOS was 99.9 / 0.1. Specifically, first, 49.9 parts by weight of TMOS and 0.1 part by weight of GPTMOS were dissolved in 50 parts by weight of methanol, and 21.0 parts by weight of a 9.88 wt% AIP aqueous solution (S22) was added thereto. Further, 3.3 parts by weight of distilled water and 8.1 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to the total of TMOS and GPTMOS was 1.95 molar equivalent, and the mixture was hydrolyzed at 10 ° C. for 5 hours. Decomposition | disassembly and condensation reaction were performed and the liquid mixture (T22) was obtained. Subsequently, after diluting the mixed solution (T22) with 567 parts by weight of distilled water and 283 parts by weight of methanol, 354 parts by weight of an aqueous solution (concentration 13% by weight) of a partially neutralized product of PAA was rapidly added. A mixed solution (U22) having a solid content concentration of 5% by weight was obtained.

  Using the mixed solution (U22), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (22).

<Laminated body (23)>
A mixed liquid (U23) was obtained at the same charging ratio as that of the laminate (18) except that the molar ratio of TMOS / GPTMOS was 70.0 / 30.0. Specifically, first, 30.0 parts by weight of TMOS and 20.0 parts by weight of GPTMOS were dissolved in 50 parts by weight of methanol, and 17.9 parts by weight of a 9.88% by weight AIP aqueous solution (S23) was added thereto. Further, 2.9 parts by weight of distilled water and 7.0 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to the total of TMOS and GPTMOS was 1.95 molar equivalent, and hydrolysis was carried out at 10 ° C. for 5 hours. Then, a condensation reaction was performed to obtain a mixed solution (T23). Subsequently, after the mixed solution (T23) was diluted with 500 parts by weight of distilled water and 310 parts by weight of methanol, 229 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight) was rapidly added while stirring. A liquid mixture (U23) having a solid content concentration of 5% by weight was obtained.

  Using the mixed solution (U23), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (23).

<Laminated body (24)>
For the production of the laminate (24), a mixture (U24) obtained by the same composition and method as the mixture (U21) obtained from the laminate (21) was used. Moreover, the laminated body was produced by performing the coating and the heat treatment in the same manner as the laminated body (1). This laminate was ionized by immersing it in a 0.1% by weight aqueous calcium acetate solution (85 ° C.) for 12 seconds, and then dried in the same manner as the laminate (1) to obtain a laminate (24).

<Laminated body (25)>
For the production of the laminate (25), a mixture (U25) obtained by the same composition and method as the mixture (U21) obtained from the laminate (21) was used. Moreover, the laminated body was produced by performing the coating and the heat treatment in the same manner as the laminated body (1). This laminate was ionized by immersion in a 0.2 wt% calcium acetate aqueous solution (85 ° C.) for 6 seconds, and then dried in the same manner as the laminate (1) to obtain a laminate (25).

<Laminated body (26)>
For the production of the laminate (26), a mixed solution (U26) obtained by the same composition and method as the mixed solution (U21) obtained from the laminate (21) was used. Moreover, the laminated body was produced by performing coating and heat treatment in the same manner as the laminated body (1). This laminate was ionized by immersion in a 0.2 wt% calcium acetate aqueous solution (85 ° C.) for 12 seconds, and then dried in the same manner as the laminate (1) to obtain a laminate (26).

<Laminated body (27)>
For the production of the laminate (27), a mixed solution (U27) obtained by the same composition and method as the mixed solution (U21) obtained from the laminate (21) was used. Moreover, the laminated body was produced by performing the coating and the heat treatment in the same manner as the laminated body (1). This laminate was ionized by immersing it in a 2% by weight aqueous magnesium acetate solution (85 ° C.) for 12 seconds, and then dried in the same manner as the laminate (1) to obtain a laminate (27).

<Laminated body (28)>
For the production of the laminate (28), a mixture (U28) obtained by the same composition and method as the mixture (U21) obtained from the laminate (21) was used. In addition, a laminate was obtained by performing coating and heat treatment in the same manner as the laminate (1). This laminate was ionized by immersing in a 2% by weight zinc acetate aqueous solution (85 ° C.) for 12 seconds, and then dried in the same manner as the laminate (1) to obtain a laminate (28).

<Laminated body (29)>
A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in the laminate (1). On the other hand, EDA was dissolved in 1N hydrochloric acid so that the molar ratio of ethylenediamine (EDA) / HCl was 1/2 to obtain an aqueous EDA hydrochloride solution. The mixed solution was prepared in the same ratio as in the laminate (7) except that the EDA hydrochloride aqueous solution was added so that the equivalent ratio of [amino group of EDA] / [carboxyl group of PAA] was 1.9 / 100. (U29) was prepared. Specifically, first, the mixture (T29) prepared by the same composition and method as the mixture (T7) of the laminate (7) was diluted with 567 parts by weight of distilled water and 283 parts by weight of methanol, and then stirred. While adding 354 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight), 12.7 parts by weight of an EDA hydrochloride aqueous solution was further added, and a mixed solution (U29) having a solid content concentration of 5% by weight was added. Obtained.

  Using the mixed solution (U29), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (29).

<Laminated body (30)>
A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in the laminate (1). On the other hand, polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA117, hereinafter sometimes abbreviated as “PVA”) is added to distilled water and heated at 85 ° C. for 3 hours so that the concentration becomes 10% by weight. Obtained.

  The mixed solution (U27) was prepared by adding the PVA aqueous solution at the same charging ratio as that of the laminate (7) except that the equivalent ratio of [hydroxyl group of PVA] / [carboxyl group of PAA] was 18.2 / 100. ) Specifically, first, a mixed solution (T30) prepared by the same composition and method as the mixed solution (T7) of the laminate (7) was diluted with 567 parts by weight of distilled water and 283 parts by weight of methanol, and then stirred. While rapidly adding 354 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight), and further adding 51 parts by weight of the 10% by weight PVA aqueous solution, a mixed solution (U30) having a solid content concentration of 5% by weight Obtained.

  Using the mixed solution (U30), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (30).

<Laminated body (31)>
A mixed solution (U31) was prepared at the same charging ratio as that of the laminate (21) except that the acid at the time of preparing the AIP aqueous solution was propionic acid. Specifically, after mixing 74 parts by weight of propionic acid and 1800 parts by weight of distilled water, 204 parts by weight of AIP (AIP / propionic acid / distilled water = 1/1/100 (molar ratio)) is stirred in this aqueous propionic acid solution. And then heated at 80 ° C. for 1 hour to obtain an AIP aqueous solution (S31) having a concentration of 9.82% by weight. A mixed liquid (U31) was obtained by the same composition and method as the mixed liquid (U21) of the laminate (18) except that this AIP aqueous solution (S31) was used.

  Using the mixed solution (U31), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (31).

<Laminated body (32)>
A mixed solution (U32) was prepared at the same charging ratio as that of the laminate (21) except that the acid at the time of preparing the AIP aqueous solution was hexanoic acid. Specifically, after 116 parts by weight of hexanoic acid and 1800 parts by weight of distilled water were mixed, 204 parts by weight of AIP (AIP / hexanoic acid / distilled water = 1/1/100 (molar ratio)) was stirred into this aqueous hexanoic acid solution. And then heated at 80 ° C. for 1 hour to obtain an AIP aqueous solution (S32) having a concentration of 9.62% by weight. A mixed liquid (U32) was obtained by the same composition and method as the mixed liquid (U21) of the laminate (21) except that this AIP aqueous solution (S32) was used.

  Using the mixed solution (U32), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (32).

<Laminated body (33)>
For the production of the laminate (33), a mixture (U33) obtained by the same composition and method as the mixture (U21) obtained from the laminate (21) was used. Except that the gas barrier layer was formed only on one side of the substrate, coating, heat treatment, ionization and drying were carried out in the same manner as in the laminate (1) to obtain a laminate (33).

<Laminated body (34)>
For the production of the laminate (34), a mixed solution (U34) obtained by the same composition and method as the mixed solution (U8) obtained from the laminate (8) was used. Further, except that the base material was a stretched polyamide film (OPA), coating, heat treatment, ionization and drying were carried out in the same manner as in the laminate (1) to obtain a laminate (34).

<Laminated body (35)>
In the laminated body (35), a mixed liquid (U35) obtained by the same composition and method as the mixed liquid (U21) obtained in the laminated body (21) was used. In addition, coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (34) to obtain a laminate (35).

<Laminated body (36)>
In the laminated body (36), a mixed liquid (U36) obtained by the same composition and method as the mixed liquid (U8) obtained in the laminated body (8) was used. In addition, coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (34) to obtain a laminate (36).

<Laminated body (37)>
The laminate (37) was produced under the same conditions as the laminate (35) except that the substrate was changed. In the production of the laminate (37), a stretched polyamide film (manufactured by Unitika Ltd., Emblem ON (trade name), thickness 25 μm, hereinafter sometimes abbreviated as “OPA ₂₅ ”) was used as the substrate.

<Laminated body (38)>
In the laminated body (38), the mixed liquid (U38) obtained by the same composition and method as the mixed liquid (U21) obtained in the laminated body (21) was used. Moreover, except having formed the gas barrier layer only in the single side | surface of a base material, coating, heat processing, ionization, and drying were performed like the laminated body (34), and the laminated body (38) was obtained.

<Laminated body (39)>
In the production of the laminate (39), the molar ratio of TMOS / GPTMOS was 89.9 / 10.1, [inorganic component derived from TMOS and GPTMOS] / [partial neutralized product of organic component of GPTMOS and PAA]. A mixed solution (T39) was prepared so that the ratio was 31.5 / 68.5. Specifically, first, 46 parts by weight of TMOS and 8 parts by weight of GPTMOS were dissolved in 50 parts by weight of methanol. To this 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 pH was 2 or less. The mixture was subjected to hydrolysis and condensation reaction for 5 hours to obtain a mixed solution (T39).

  Subsequently, a partially neutralized aqueous solution of PAA was prepared in the same manner as in the laminate (1). Next, after diluting the mixed liquid (T36) with 61 parts by weight of distilled water, 308 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight) was rapidly added while stirring to obtain a solid content concentration of 13% by weight. A liquid mixture (U39) was obtained.

  On the other hand, a two-component anchor coating agent dissolved in 67 parts by weight of ethyl acetate (Mitsui Takeda Chemical Co., Ltd .: Takelac A-626 (trade name) 1 part by weight and Takenate A-50 (trade name) 2 parts by weight) Was coated on a stretched polyethylene terephthalate film (“PET” described above) and dried to prepare a substrate (AC (0.1 μm) / PET (12 μm)) having an anchor coat layer. On the anchor coat layer of this substrate, the mixed solution (U39) was coated with a bar coater so that the thickness after drying was 1.0 μm, and dried at 120 ° C. for 5 minutes. In the same procedure, both sides of the substrate were coated to obtain a laminate. This laminate was aged at 40 ° C. for 3 days. Subsequently, the laminate was heat-treated at 180 ° C. for 5 minutes using a dryer. Next, the laminate was immersed in a 2% by weight calcium acetate aqueous solution (85 ° C.) for 12 seconds and then dried at 50 ° C. for 5 minutes. In this way, a laminate (39) having a structure of gas barrier layer (1.0 μm) / AC (0.1 μm) / PET (12 μm) / AC (0.1 μm) / gas barrier layer (1.0 μm) is obtained. It was.

<Laminated body (40)>
For the production of the laminate (40), a mixed solution (U40) obtained by the same composition and method as the mixed solution (U39) obtained from the laminate (39) was used. Also, except that the base material was OPA, coating, heat treatment and ionization drying were performed in the same manner as in the laminate (1) to obtain a laminate (40).

<Laminated body (41)>
A mixed solution (U41) was obtained in the same manner as in the laminate (39) except that the solid content concentration was changed to 5% by weight. First, after the liquid mixture (T41) prepared by the same composition and method as the liquid mixture (T39) of the laminate (39) was diluted with 542 parts by weight of distilled water and 293 parts by weight of methanol, 308 parts by weight of an aqueous solution of a Japanese product (concentration 13% by weight) was quickly added to obtain a mixed solution (U41) having a solid content concentration of 5% by weight.

  Using the mixed solution (U41), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (41).

<Laminated body (42)>
For the production of the laminate (42), a mixed solution (U42) obtained by the same composition and method as the mixed solution (U41) obtained from the laminate (41) was used. In addition, coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (34) to obtain a laminate (42).

<Laminated body (43)>
A partially neutralized aqueous solution of PAA and an AIP aqueous solution were prepared in the same manner as in the laminate (1). A liquid mixture (U43) was prepared so that the weight ratio of [inorganic component derived from AIP] / [partially neutralized product of PAA] was 1.0 / 99.0 without adding TMOS and GPTMOS. Specifically, 100 parts by weight of a partially neutralized aqueous solution of PAA (concentration 5% by weight) is quickly added to 2.1 parts by weight of the 9.88% by weight AIP aqueous solution (S43), and the mixed solution (U43) is added. Obtained.

  Using the mixed solution (U43), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (43).

<Laminated body (44)>
A partially neutralized aqueous solution of PAA was prepared in the same manner as in the laminate (1). A mixed solution (U44) was prepared so that the weight ratio of [inorganic component derived from titanium lactate] / [partially neutralized product of PAA] was 0.9 / 99.1. Specifically, 1.6 parts by weight of an isopropyl alcohol solution of titanium lactate (concentration 10% by weight) is added to 100 parts by weight of an aqueous solution of partially neutralized PAA (concentration 5% by weight), and a mixed solution (U44) Got.

  Using the mixed solution (U44), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (44).

<Laminated body (45)>
The molar ratio of Al / Si was 40.4 / 59.6, and the weight ratio of [inorganic component derived from TMOS and AIP] / [partially neutralized product of PAA] was 40.3 / 59.7. A mixed solution (U45) was prepared with the same charging ratio as in the laminate (3) except for the above. Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 461 parts by weight of a 9.88 wt% AIP aqueous solution (S45) was added thereto. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalent, and hydrolysis and condensation reaction was performed at 10 ° C. for 5 hours. To obtain a mixed solution (T45). Subsequently, after the mixed solution (T45) 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. A liquid mixture (U45) having a solid content concentration of 5% by weight was obtained.

  Using the mixed solution (U45), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (45).

<Laminated body (46)>
The molar ratio of Al / Si was 0.06 / 99.94, and the weight ratio of [inorganic component derived from TMOS and AIP] / [partially neutralized product of PAA] was 70.0 / 30.0. Except for the above, a mixed solution (U46) was prepared at the same charging ratio as in the laminate (3). Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 0.4 part by weight of a 9.88 wt% AIP aqueous solution (S46) was added thereto. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalent, and hydrolysis and condensation reaction was performed at 10 ° C. for 5 hours. And a liquid mixture (T46) was obtained. Subsequently, the mixed liquid (T46) was diluted with 243 parts by weight of distilled water and 144 parts by weight of methanol, and then 65 parts by weight of a partially neutralized aqueous solution of PAA (concentration 13% by weight) was rapidly added while stirring. A mixed solution (U46) having a partial concentration of 5% by weight was obtained.

  Using the mixed solution (U46), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (46).

<Laminated body (47)>
A mixed solution (U47) was prepared by changing the reaction time only at the same charging ratio as in the laminate (46).

  Specifically, first, 50 parts by weight of TMOS was dissolved in 50 parts by weight of methanol, and 0.4 part by weight of a 9.88 wt% AIP aqueous solution (S47) was added thereto. Further, 3.3 parts by weight of distilled water and 8.2 parts by weight of 0.1N hydrochloric acid were added so that the ratio of water to TMOS was 1.95 molar equivalent, and hydrolysis and condensation reaction was performed at 10 ° C. for 1 hour. And a mixed solution (T47) was obtained. Subsequently, after the mixed liquid (T47) was diluted with 243 parts by weight of distilled water and 144 parts by weight of methanol, 65 parts by weight of an aqueous solution (partial concentration 13% by weight) of a partially neutralized PAA was rapidly added while stirring. A liquid mixture (U47) having a solid content concentration of 5% by weight was obtained.

  Using the mixed solution (U47), coating, heat treatment, ionization and drying were performed in the same manner as in the laminate (1) to obtain a laminate (47).

<Laminated body (48)>
For the production of the laminate (48), a mixture (U48) obtained by the same composition and method as the mixture (U21) obtained from the laminate (21) was used. In addition, coating and heat treatment were performed in the same manner as in the laminate (1) to produce a laminate (48).

[Evaluation results of laminate]
The produced laminate was evaluated by the method described above. In addition, evaluation about a laminated body (37) was not performed. The stretched polyethylene terephthalate film (PET) and stretched polyamide film (OPA) used as the substrate of the laminate were evaluated in the same manner as the laminate. The production conditions for the laminate are shown in Table 1.

  Table 2 shows the evaluation results of the laminate and the substrate.

  The total thickness of the gas barrier layers of the laminate (39) is 2.0 μm. Thus, when the total thickness of the gas barrier layer is large (for example, larger than 1.0 μm), the physical properties of the laminate are greatly different from the physical properties of the base material (PET), and the workability is reduced. End up. Therefore, when the gas barrier layer is made thick, there arises a problem that productivity is lowered. On the other hand, a laminate having a thin total gas barrier layer, such as laminates (1) to (33), exhibits physical properties close to that of the base material (PET) and has good workability. Further, as will be described later, in order to increase the durability of the gas barrier layer against bending, it is necessary to make the gas barrier layer thin.

[Production of laminate]
A laminate was produced using the laminate (1). First, on each of the stretched polyamide film (OPA) and the unstretched polypropylene film (CPP), a two-pack type adhesive (Mitsui Takeda Chemical Co., Ltd., A-385 (trade name) and A-50 (product) Name)) was coated and dried. And these and a laminated body (1) were laminated. Thus, a laminate (1) having a structure of laminate (1) / adhesive / OPA / adhesive / CPP was obtained. In addition, other laminates were produced and evaluated in the same manner as the laminate (1). Table 3 shows the laminate used for the production of the laminate and the evaluation results of the laminate.

[Production and evaluation of pouch with spout]
A pouch with a spout was prepared and evaluated using the above-described laminate. Evaluation of the pouch with a spout was carried out by the following methods (1) to (4).

(1) Oxygen permeability before retort treatment For the flat pouch-type pouches obtained in Examples and Comparative Examples (hereinafter sometimes simply referred to as “pouches”), oxygen permeation before retort treatment is performed by the following method. The degree was measured.

  First, set a metal jig to which two metal pipes for carrier gas are connected to the spout opening of the pouch, and use epoxy adhesive so that gas does not leak from the gap between the metal jig and the spout. A metal jig was fixed to the spout mouth. Next, the opposite end of the metal pipe was connected to an oxygen permeation amount measuring device ("MOCON OX-TRAN 2/20" manufactured by Modern Control). That is, the carrier gas is discharged from one of the metal pipes into the pouch with the spout, passes through the pouch with the spout, and then flows from the other metal pipe into the oxygen gas sensor of the oxygen transmission amount measuring device.

  Subsequently, the pouch attached with the metal pipe was covered with a bag, and the bag was fixed to two metal pipes with a string. The bag was produced by heat-sealing a laminated film having a laminated structure of polyester / adhesive layer / EVOH layer / adhesive layer / PO layer. Next, the airtightness was improved by filling the gap between the bag and the metal pipe with an epoxy resin. Next, a hole is made in one place of the bag, a pipe for supplying gas is put in the hole, and the bag and the pipe are fixed using adhesive tape so that outside air does not flow in between the bag and the pipe. did.

  Subsequently, nitrogen gas containing 2% by volume of hydrogen gas was allowed to flow as a carrier gas through the pipe and metal pipe into the bag and pouch. Part of the gas flowing into the bag passes through the pouch and flows into the inside of the pouch, the other part passes through the bag and flows out, and the other part is connected at two locations. Leaked from the outside. The oxygen gas contained in the carrier gas was carried to the sensor unit by the carrier gas, and the oxygen concentration was measured. The carrier gas was kept flowing in the bag and the pouch until the oxygen concentration reached a constant value. The oxygen concentration at the time when the oxygen concentration became constant was set as the zero point of oxygen permeability.

Thereafter, the carrier gas flowing in the bag was switched to a conditioned oxygen gas. In other words, nitrogen gas flowed inside the pouch and oxygen gas flowed outside the pouch. The oxygen gas that permeated from the outside to the inside of the pouch was carried to the oxygen gas sensor by the carrier gas flowing inside the pouch, and the oxygen concentration was measured. From the oxygen concentration measured at this time, the oxygen permeability (unit: cm ³ / (m ² · day · atm)) of the pouch with a spout before the retort treatment was calculated. The measurement was performed under the conditions of a temperature of 20 ° C., a humidity of 85% RH, an oxygen pressure of 1 atm, and a carrier gas pressure of 1 atm. As the carrier gas, nitrogen gas containing 2% by volume of hydrogen gas was used.

  Subsequently, the oxygen permeability of the spout itself was measured by the following method. First, the spout part which has come out of the pouch from the pouch with a spout was cut out. Subsequently, the spout mouth was sealed with aluminum foil. After that, set the metal jig to which two metal pipes for carrier gas are connected from the unsealed side of the spout, and use epoxy adhesive to leak gas from the gap between the metal jig and the spout. The metal jig was fixed to the spout so that there was no. Next, the opposite end of the metal pipe was connected to an oxygen permeation amount measuring device ("MOCON OX-TRAN 2/20" manufactured by Modern Control). That is, the carrier gas flows into the spout from one of the metal pipes, flows through the spout, and then flows into the oxygen gas sensor from the other metal pipe.

  Subsequently, the spout attached with the metal pipe was covered with a bag. The bag was produced by heat-sealing a laminated film having a laminated structure of polyester / adhesive layer / EVOH layer / adhesive layer / PO layer. Next, the bag was fixed to two metal pipes with a string. Airtightness was improved by filling the gap between the bag and the metal pipe with epoxy resin. A hole was made in one place of the bag, a pipe for supplying gas was put in the hole, and the bag and the pipe were fixed using an adhesive tape so that outside air would not flow between the bag and the pipe.

  Subsequently, nitrogen gas containing 2% by volume of hydrogen gas was allowed to flow as a carrier gas through the pipe and metal pipe into the bag and spout. Part of the gas that has flowed into the bag passes through the spout and flows into the spout, the other part passes through the bag and flows out, and part of the gas flows out of the two connections. Leaked to. The oxygen gas contained in the carrier gas was carried to the sensor unit by the carrier gas, and the oxygen concentration was measured. Then, the carrier gas was kept flowing in the bag and the spout until the oxygen concentration reached a constant value. The oxygen concentration at the time when the oxygen concentration became constant was set as the zero point of oxygen permeability.

Thereafter, the carrier gas flowing in the bag was switched to a conditioned oxygen gas. That is, nitrogen gas flows inside the spout and oxygen gas flows outside the spout. The oxygen gas that permeated from the outside of the spout to the inside was carried to the oxygen gas sensor by the carrier gas flowing inside the spout, and the oxygen concentration was measured. From the oxygen concentration measured at this time, the oxygen permeability (unit: cm ³ / (m ² · day · atm)) of the spout before the retort treatment was calculated. Measurement was performed under the conditions of a temperature of 20 ° C., a humidity of 85% RH, an oxygen pressure of 1 atm, and a carrier gas pressure of 1 atm. As the carrier gas, nitrogen gas containing 2% by volume of hydrogen gas was used. The surface area of the spout portion outside the pouch was 9 cm ² , and the oxygen permeability was 28 cm ³ / (m ² · day · atm).

Subsequently, the oxygen permeability of the gas barrier laminate was calculated. The gas barrier laminate of the pouch with a spout produced in the examples and comparative examples has a size of 10 cm × 12 cm, and a width of 0.5 cm on the outer periphery thereof was heat-sealed. That is, the surface area of the gas barrier laminate was 9 cm × 11 cm = 99 cm ² .

From the oxygen permeability of each of the pouch with spout and the spout measured by the above method, the oxygen permeability of the gas barrier laminate before the retort treatment was calculated using the following equation.
[Oxygen permeability of pouch with spout] = ([oxygen permeability of gas barrier laminate] × [surface area of gas barrier laminate] + [oxygen permeability of spout] × [surface area of spout]) / ([gas barrier property Laminate surface area] + [spout surface area])

Specifically, when the oxygen permeability of the pouch with a spout is 3.00 cm ³ / (m ² · day · atm), the oxygen permeability of the gas barrier laminate can be calculated as follows.
3.00 = ([Oxygen permeability of gas barrier laminate] × 99 + 28 × 9) / (99 + 9)
[Oxygen permeability of gas barrier laminate] = (3 × 10 8 −28 × 9) /99=0.73 cm ³ / (m ² · day · atm)

(2) Oxygen permeability after retort treatment The flat pouch-type pouch with spout obtained in Examples and Comparative Examples was filled with 100 mL of distilled water, and the retort treatment device (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, the heating was stopped, and when the internal temperature of the retort treatment device reached 60 ° C., the pouch with a spout was taken out from the retort treatment device. Then, the pouch with spout was left for 1 hour in a room at 20 ° C. and 65% RH. One hour later, water was extracted from the spout portion of the pouch with spout. The oxygen permeability of the pouch with spout after the retort treatment thus obtained was measured by the same method and conditions as the oxygen permeability before the retort treatment.

The oxygen permeability of the spout was also measured by the same method and conditions as the oxygen permeability before the retort treatment. The oxygen permeability of the spout did not change before and after the retort treatment, and was 28 cm ³ / (m ² · day · atm). Subsequently, the oxygen permeability of the gas barrier laminate after the retort treatment was calculated based on the above formula.

(3) Oxygen permeability after retort treatment and after bending test The flat pouch-type pouch with spout obtained in the examples and comparative examples was filled with 100 mL of distilled water, and the retort treatment device (manufactured by Nisaka Seisakusho, Flavor). Ace RCS-60) and subjected to retort treatment under the conditions of 120 ° C., 30 minutes, 0.15 MPa. After the retort treatment, the heating was stopped, and when the internal temperature of the retort treatment device reached 60 ° C., the pouch with a spout was taken out from the retort treatment device. Then, the pouch with spout was left for 1 hour in a room at 20 ° C. and 65% RH.

  Thereafter, the pouch with a spout after the retort treatment was dropped five times from the height of 1.5 m from the side of the pouch, that is, the heat seal side. In this way, a bending test for bending the pouch was performed. Subsequently, water was extracted from the spout portion of the pouch with the spout after the bending test. The oxygen permeability of the gas barrier laminate of the spout with pouch thus obtained was measured by the same method and conditions as the oxygen permeability before the retort treatment.

(4) Appearance after retort treatment The pouch with spout obtained in the examples and comparative examples was filled with water, and they were put into a retort treatment device (manufactured by Nisaka Seisakusho, Flavor Ace RCS-60). The retort treatment was performed under the condition of 0.25 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.

  Then, the appearance of the pouch is observed. If there is no haze as before the retort, it is “very good (◎)”. If it is slightly cloudy but there is no practical problem, “good (○)”. When it was clearly cloudy, it was judged as “bad (×)”.

<Example 1>
Stretched polyamide film (manufactured by Unitika Ltd., Emblem ON-BC (trade name), thickness 15 μm, OPA) and unstretched polypropylene film (Tosero Co., Ltd., RXC-21 (trade name), thickness 50 μm, CPP ) Was coated with a two-component adhesive (Mitsui Takeda Chemical Co., Ltd., A-385 (trade name) and A-50 (trade name)) and dried. And these and the said laminated body (6) were laminated. Thus, a laminate (A1) having a structure of laminate (6) / adhesive / OPA / adhesive / CPP was obtained.

  Two laminates (A1) were cut into a size of 12 cm × 10 cm. Subsequently, the two laminated bodies (A1) that were cut were overlapped so that the CPP was inside, the periphery was heat sealed, and a polypropylene spout was attached by heat sealing. In this manner, the flat pouch-type pouch with a spout of Example 1 was produced.

<Examples 2 to 18>
A laminate having a structure of laminate / adhesive / OPA / adhesive / CPP was obtained in the same manner as in Example 1 except that the other laminate was used instead of the laminate (6). A flat pouch-type pouch with a spout of Examples 2 to 18 was produced in the same manner as in Example 1 except that the obtained laminate was used instead of the laminate (A1). Table 4 shows the numbers of the laminates used.

<Example 19>
After coating and drying a two-component adhesive (Mitsui Takeda Chemical Co., Ltd., A-385 (trade name) and A-50 (trade name)) on an unstretched polypropylene film (CPP) CPP and the laminate (35) were laminated. Thus, a laminate (A19) having a structure of laminate (35) / adhesive / CPP was obtained. A flat pouch-type pouch with a spout of Example 19 was produced in the same manner as in Example 1 except that the laminate (A19) was used instead of the laminate (A1).

<Example 20>
Two-component adhesive (Mitsui Takeda Chemical Co., Ltd.) on each of a stretched polyethylene terephthalate film (manufactured by Toray Industries, Inc., Lumirror P60 (trade name), thickness 12 μm, PET) and unstretched polypropylene film (CPP) After making and drying company-made A-385 (brand name) and A-50 (brand name), they and the laminated body (35) were laminated. Thus, a laminate (A20) having a structure of PET / adhesive / laminate (35) / adhesive / CPP was obtained. A flat pouch-type pouch with a spout of Example 20 was produced in the same manner as in Example 1 except that the laminate (A20) was used instead of the laminate (A1).

<Comparative Examples 1, 3, 5-8>
A laminate having a structure of laminate / adhesive / OPA / adhesive / CPP was obtained in the same manner as in Example 1 except that the other laminate was used instead of the laminate (6). Except that the obtained laminate was used instead of the laminate (A1), flat pouch-type pouches with spouts of Comparative Examples 1, 3, and 5 to 8 were produced in the same manner as in Example 1. Table 4 shows the numbers of the laminates used.

<Comparative Examples 2 and 4>
A laminate having a structure of laminate / adhesive / CPP was obtained in the same manner as in Example 17 except that another laminate was used instead of the laminate (35). A flat pouch-type pouch with a spout of Comparative Examples 2 and 4 was produced in the same manner as in Example 17 except that the obtained laminate was used instead of the laminate (A17). Table 4 shows the numbers of the laminates used.

  Table 4 shows the numbers of the laminates used in the pouches with spouts of Examples and Comparative Examples, and the conditions for producing the laminates.

  Table 5 shows the evaluation results of the pouches with spouts of Examples and Comparative Examples.

  As shown in Table 5, the pouches with spouts of the examples exhibited good oxygen barrier properties before the retort treatment, after the retort treatment, and after the bending test. Moreover, the appearance of the pouch with a spout of an Example was favorable also after the severe retort processing which is not normally performed at 135 degreeC for 60 minutes.

As shown in Examples and Comparative Examples, the ratio of [number of moles of M ¹ atom derived from compound (A)] / [number of moles of Si atom derived from compound (B)] was 0.1 / 99. When it was in the range of 9 to 35.0 / 65.0, a pouch having excellent oxygen barrier properties before and after the retort treatment and excellent appearance after the retort treatment was obtained. This ratio is preferably in the range of 1.2 / 98.8 to 30.0 / 70.0, and preferably in the range of 1.9 / 98.1 to 30.0 / 70.0. More preferably, it is in the range of 2.8 / 97.2 to 30.0 / 70.0.

  As shown in the Examples, [weight of inorganic component derived from compound (L)] / [total weight of organic component derived from compound (L) and weight of organic component derived from polymer (X) ] Is preferably in the range of 20.0 / 80.0 to 80.0 / 20.0, and more preferably in the range of 30.5 / 69.5 to 70/30.

  As shown in the examples, in order to obtain excellent oxygen barrier permeability, [number of moles of Si atoms derived from the compound represented by formula (II)] / [compound represented by formula (III) Is preferably in the range of 99.5 / 0.5 to 80.0 / 20.0, more preferably 98.0 / 2.0 to 89.9 / 10. More preferably, it is in the range of 1.

  As shown in the Examples, in order to obtain excellent oxygen barrier properties, it is preferable that 60 mol% or more of the —COO— group is neutralized with a divalent or higher metal ion.

  As shown in the Examples, good results were obtained using either PET or OPA as the substrate. The pouch using PET as the substrate showed better performance than the pouch using OPA as the substrate. In Examples 19 and 20, the films other than the gas barrier laminate did not affect the performance.

  The spout pouches of Comparative Examples 1 and 2 had relatively good oxygen barrier properties before and after retorting. However, this is because the sum of the gas barrier layers of Comparative Examples 1 and 2 is as thick as 2 μm. In Comparative Examples 1 and 2 where the gas barrier layer is thick, the durability of the gas barrier layer against bending is low, and the oxygen barrier property is greatly reduced by the bending test.

  In Comparative Examples 3 to 8 in which the thickness of the gas barrier layer was the same as that of the example, the oxygen barrier property was low at any stage before the retort treatment, after the retort treatment, and after the bending test. In addition, the spout with a spout of the comparative example did not change in appearance after retorting at 120 ° C. under a general condition of 30 minutes, but after retorting under a severe condition of 135 ° C. for 60 minutes. Decreased. Moreover, the pouch with a spout of the comparative example 8 had delamination by the retort process.

  As described above, like the evaluation of the gas barrier laminate alone, the pouch with a spout of the present invention using a predetermined gas barrier layer exhibited excellent characteristics.

  The present invention can be used for a pouch with a spout. The pouch of the present invention can be used as a container for various liquid substances. For example, the pouch of the present invention can be used as a container for liquid drinks (for example, soft drinks), jelly drinks, yogurt, fruit sauces, seasonings, functional water, and liquid foods. The pouch of the present invention can also be preferably used as a container for liquid pharmaceuticals such as amino acid infusions, electrolyte infusions, sugar infusions, and infusion fat emulsions.

10, 20 Pouch with spout 11, 21 Spout

Claims (7)

A pouch with a spout formed using a gas barrier laminate,
The gas barrier laminate includes a substrate and at least one gas barrier layer laminated on the substrate,
The layer comprises a hydrolysis condensate of at least one compound (L) containing a hydrolyzable characteristic group, and a polymer containing at least one functional group selected from a carboxyl group and a carboxylic anhydride group. Comprising a neutralized product of (X),
The compound (L) includes a compound (A) and a compound (B) containing Si to which a hydrolyzable characteristic group is bonded,
The compound (A) is at least one compound represented by the following formula (I):
M ¹ X ¹ _m Y ¹ _nm (I)
[In Formula (I), M ¹ represents any one selected from Al, Ti, and Zr. X ¹ represents any one selected from F, Cl, Br, I, OR ¹ , R ² COO, R ³ COCHCOR ⁴ , and NO ₃ . Y ¹ represents any one selected from F, Cl, Br, I, OR ⁵ , R ⁶ COO, R ⁷ COCHCOR ⁸ , NO ₃ and R ⁹ . R ¹ , R ² , R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group. ^{R 3, R 4, R 7} , R 8 and R ⁹ independently represent an alkyl group. n is equal to the valence of M ¹ . m represents an integer of 1 to n. ]
The compound (B) includes at least one compound represented by the following formula (II):
Si (OR ¹⁰ ) _p R ¹¹ _4-pq X ² _q (II)
[In the formula (II), R ¹⁰ represents an alkyl group. R ¹¹ represents an alkyl group, an aralkyl group, an aryl group or an alkenyl group. X ² represents a halogen atom. p and q represent the integer of 0-4 each independently. 1 ≦ p + q ≦ 4. ]
At least a part of —COO— group contained in the functional group of the polymer (X) is neutralized with a divalent or higher metal ion,
The proportion of the compound represented by the formula (II) in the compound (B) is 80 mol% or more,
In the composition, a ratio of [number of moles of the M ¹ atom derived from the compound (A)] / [number of moles of Si atom derived from the compound (B)] is 0.1 / 99.9 to 35. Spouted pouch in the range of 0.0 / 65.0. The compound (B) further includes at least one compound represented by the following formula (III):
Si (OR ¹² ) _r X ³ _s Z ³ _4-rs (III)
[In the formula (III), R ¹² represents an alkyl group. X ³ represents a halogen atom. Z ³ represents an alkyl group substituted with a functional group having reactivity with a carboxyl group. r and s each independently represent an integer of 0 to 3. 1 ≦ r + s ≦ 3. ]
The ratio [number of moles of Si atoms derived from the compound represented by the formula (II)] / [number of moles of Si atoms derived from the compound represented by the formula (III)] was 99.5 / 0. The pouch with a spout according to claim 1, which is in the range of 0.5 to 80.0 / 20.0. The pouch with a spout according to claim 1 or 2, wherein the M ¹ is Al.   The ratio of [weight of inorganic component derived from the compound (L)] / [total weight of organic component derived from the compound (L) and weight of organic component derived from the polymer (X)] is: The pouch with a spout according to any one of claims 1 to 3, which is in the range of 20.0 / 80.0 to 80.0 / 20.0.   The ratio of [weight of inorganic component derived from the compound (L)] / [total weight of organic component derived from the compound (L) and weight of organic component derived from the polymer (X)] is: The pouch with a spout according to any one of claims 1 to 3, wherein the pouch is in the range of 30.5 / 69.5 to 70.0 / 30.0.   The pouch with a spout according to any one of claims 1 to 5, wherein 60 mol% or more of -COO- groups contained in the functional group of the polymer (X) are neutralized by the metal ions.   The pouch with a spout according to any one of claims 1 to 6, wherein the gas barrier laminate includes an unstretched polypropylene layer disposed on the inner side of the outermost layer.

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