JP6983599B2 - Gas barrier laminates and packages - Google Patents

Description

The present invention relates to a gas barrier laminate and a package.

Generally, as a gas barrier material, a laminate in which an inorganic material layer, which is a gas barrier layer, is provided on a base material layer is used.
However, this inorganic layer is vulnerable to friction and the like, and such a gas barrier laminate has a gas barrier property due to cracks in the inorganic layer due to rubbing and elongation during post-processing printing, laminating, or filling of contents. May decrease.
Therefore, as a gas barrier material, a laminate using an organic layer as a gas barrier layer is also used.

As a gas barrier material using an organic layer as a gas barrier layer, a laminate having a gas barrier layer formed of a mixture containing a polycarboxylic acid and a polyamine compound is known.
Examples of the technique relating to such a gas barrier laminate include those described in Patent Document 1 (Japanese Patent Laid-Open No. 2005-225940) and Patent Document 2 (Japanese Patent Laid-Open No. 2013-10857).

Patent Document 1 discloses a gas barrier film having a gas barrier layer formed of a polycarboxylic acid and a polyamine and / or a polyol, and having a degree of cross-linking of the polycarboxylic acid of 40% or more.
Patent Document 1 describes that such a gas barrier film has excellent gas barrier properties even under high humidity conditions as well as under low humidity conditions.

In Patent Document 2, polyamine and polycarboxylic acid are added to at least one surface of a base material made of a plastic film in a weight ratio of polyamine / polycarboxylic acid = 12.5 / 87.5 to 27.5 / 72.5. A film coated with a mixture thereof is disclosed.
Patent Document 2 describes that such a gas barrier film is excellent in gas barrier property, particularly oxygen blocking property, and also excellent in flexibility, transparency, moisture resistance, chemical resistance and the like even after boiling treatment.

Japanese Unexamined Patent Publication No. 2005-225940 Japanese Unexamined Patent Publication No. 2013-10857

The technical standards required for various properties of gas barrier materials are becoming higher and higher. According to the studies by the present inventors, the gas barrier film described in Patent Documents 1 and 2 has room for improvement in gas barrier property after retort treatment and gas barrier property when retort treatment is applied after bending load is applied. It became clear.

INDUSTRIAL APPLICABILITY The present invention provides a gas barrier laminated body having excellent gas barrier properties even when the retort treatment is performed after the retort treatment or after a bending load is applied.

According to the present invention, the following gas barrier laminates and packages are provided.
[1]
With the base material layer,
A gas barrier polymer layer provided on at least one surface of the base material layer and
It is a gas barrier laminated body containing
The gas barrier polymer layer is formed by heat-curing a mixture containing a polycarboxylic acid and a polyamine compound.
In the infrared absorption spectrum of the gas barrier polymer layer,
The total peak area in the range of absorption band 1493 cm ^-1 or more and 1780 cm ^{-1 or less is defined as A.}
When the total peak area in the range of the absorption band 1598cm ^-1 or 1690 cm ^-1 and is B,
The area ratio of the amide bond represented by (B / A) is 0.400 or less, and the area ratio is 0.400 or less.
The thickness of the gas barrier polymer layer is 0.01 μm or more and 0.45 μm or less.
A sample obtained by subjecting the gas barrier laminate to a gelbo treatment under the following condition 1 and then retort-treated under the following condition 2 and a sample obtained by retort-treating under the following condition 2. A gas barrier laminate having an oxygen permeability at 20 ± 2 ° C. and 90 ± 5% RH of 150 mL / (m ² · day · MPa) or less.
(Condition 1) Using a gelboflex tester (manufactured by Tester Sangyo Co., Ltd.), bending treatment was performed 10 times under the conditions of an atmospheric temperature of 23 ± 2 ° C. and 50 ± 5% RH.
(Condition 2) Retort treatment at 130 ° C for 30 minutes with a high-temperature and high-pressure retort sterilizer.
[2]
The gas barrier laminate according to the above [1], wherein an inorganic layer is provided between the substrate layer and the gas barrier polymer layer.
[3]
The gas barrier laminate according to the above [2], wherein the inorganic layer is formed of one or more kinds of inorganic substances selected from the group consisting of silicon oxide, aluminum oxide and aluminum.
[ 4 ]
In the infrared absorption spectrum of the gas barrier polymer layer,
When the total peak area in the range of the absorption band 1690 cm ^-1 or 1780 cm ^-1 and as C,
(C / A) the area of carboxylic acids ratio represented by is 0.150 or more 0.280 or less, the above-mentioned [1] to [3] gas barrier layered body according to any one.
[ 5 ]
In the infrared absorption spectrum of the gas barrier polymer layer,
When the total peak area in the range of the absorption band 1493cm ^-1 or 1598cm ^-1 to as D,
The gas barrier laminate according to any one of [1 ] to [ 4 ] above, wherein the area ratio of the carboxylate represented by (D / A) is 0.300 or more and 0.600 or less.
[ 6 ]
((Number of moles of -COO- group contained in the polycarboxylic acid in the mixture) / (Number of moles of amino group contained in the polyamine compound in the mixture)) is 100/70 or more and 100/40 or less. The gas barrier laminate according to any one of the above [1] to [ 5].
[ 7 ]
The above [1 ] to [], wherein the polycarboxylic acid contains one or more polymers selected from the group consisting of polyacrylic acid, polymethacrylic acid, and a copolymer of acrylic acid and methacrylic acid. 6 ] The gas barrier laminate according to any one of the following items.
[ 8 ]
The gas barrier laminate according to any one of [1 ] to [ 7 ] above, wherein the polyamine compound contains polyethyleneimine.
[ 9 ]
A package containing the gas barrier laminate according to any one of the above [1] to [ 8].

According to the present invention, it is possible to provide a gas barrier laminated body having excellent gas barrier properties even when the retort treatment is performed after the retort treatment or after a bending load is applied.

It is sectional drawing which shows typically the structure of the gas barrier laminated body in embodiment. It is sectional drawing which shows typically the structure of the gas barrier laminated body in embodiment.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. The figure is a schematic view and does not match the actual dimensional ratio. In addition, "~" between the numbers in the sentence indicates the following from the above unless otherwise specified.

(Gas barrier laminate)
FIG. 1 is a cross-sectional view schematically showing the configuration of the gas barrier laminated body 100 in the present embodiment.
In FIG. 1, the gas barrier laminate 100 includes a substrate layer 101 and a gas barrier polymer layer 103 provided on at least one surface of the substrate layer 101.
Further, as shown in FIG. 2, in the gas barrier laminated body 100, the inorganic layer 102 may be further laminated between the base material layer 101 and the gas barrier polymer layer 103. Thereby, the oxygen barrier property can be further improved.

In the gas barrier laminate 100, a sample obtained by gelvo treatment under the following condition 1 and then retort-treated under the following condition 2 and a sample obtained by the retort treatment under the following condition 2 The oxygen permeability at 20 ± 2 ° C. and 90 ± 5% RH is 150 mL / (m ² · day · MPa) or less.
(Condition 1) Using a gelboflex tester (manufactured by Tester Sangyo Co., Ltd.), bending treatment was performed 10 times under the conditions of an atmospheric temperature of 23 ± 2 ° C. and 50 ± 5% RH.
(Condition 2) Retort treatment at 130 ° C for 30 minutes with a high-temperature and high-pressure retort sterilizer.

Since the oxygen permeability of the gas barrier laminate 100 is within a specific range, it is excellent in bending resistance and gas barrier property after the retort treatment and after the retort treatment after the bending treatment.
20 ± of a sample obtained by subjecting the gas barrier laminate 100 to a gelbo treatment under the above condition 1 and then retorting under the above condition 2 and a sample obtained by retorting under the following condition 2 The oxygen permeability at 2 ° C. and 90 ± 5% RH is 150 mL / (m ² · day · MPa) or less, preferably 140 mL / (m ² · day · MPa) or less, more preferably 135 mL. / (M ² · day · MPa) or less, more preferably 100 mL / (m ² · day · MPa) or less.
The lower limit of the oxygen permeability is at ^{0mL / (m 2 · day ·} MPa) or higher, it may be e.g. ^{10mL / (m 2 · day ·} MPa) or higher.
The gas barrier laminate 100 having the oxygen permeability in a specific range can be obtained, for example, by selecting a specific material for the gas barrier polymer layer 103 and controlling the production conditions thereof. More specifically, the oxygen permeability of the sample obtained by the gelbo treatment under the above condition 1 and then the retort treatment under the above condition 2 at 20 ± 2 ° C. and 90 ± 5% RH is within a specific range. As a design guideline for providing a certain gas barrier laminate 100, the gas barrier polymer layer 103 is configured to be a layer formed by heat-curing a mixture containing a polycarboxylic acid and a polyamine compound, and a gas barrier polymer layer. The selection of specific conditions as the heating method, heating temperature and heating time of 103 may be mentioned.

Hereinafter, each layer constituting the gas barrier laminated body 100 will be described.
In the following, an example is a configuration in which the gas barrier polymer layer 103 is a layer formed by heat-curing a mixture containing a polycarboxylic acid and a polyamine compound (hereinafter, the mixture is also referred to as a “gas barrier coating material”). Explain to.
Here, the layer formed by heat-curing a mixture containing a polycarboxylic acid and a polyamine compound means a layer composed of an amide crosslinked product of the mixture containing the polycarboxylic acid and the polyamine compound.

(Gas barrier polymer layer)
The gas barrier polymer layer 103 is formed by heating and curing a mixture containing, for example, a polycarboxylic acid and a polyamine compound.
In the gas barrier polymer layer 103, absorption of the unreacted carboxylic acid based on νC = O in the infrared absorption spectrum is ^{observed in the vicinity of 1700 cm -1} , and absorption of the amide bond having a crosslinked structure based on νC = O is 1630. It is found around ~ 1685 cm ^-1 and absorption of the carboxylate based on νC = O is seen around ^{1540-1560 cm -1.
That is, the total peak area A in the range of the absorption band 1493 cm -1} or more and 1780 cm ^-1 or less in the infrared absorption spectrum of the gas barrier polymer layer 103 represents an index of the total amount of the carboxylic acid, the amide bond and the carboxylate. Total peak area B in the range of the absorption band 1598cm ^-1 or 1690 cm ^-1 represents an indication of the presence of an amide bond. Total peak area C in the following ranges absorption band 1690 cm ^-1 or 1780 cm ^-1 represents an indication of the presence of unreacted carboxylic acid. The total peak area D in the range of 1493cm ^-1 or 1598cm ^-1 or less, carboxylate, i.e. believed to represent the indication of the presence of ionic crosslinking of the carboxyl group and an amino group.

In this embodiment, the total peak areas A to D can be measured by the following procedure.
First, a 1 cm × 3 cm measurement sample is cut out from the gas barrier polymer layer 103. Next, the infrared absorption spectrum of the surface of the gas barrier polymer layer 103 is obtained by infrared total reflection measurement (ATR method). From the obtained infrared absorption spectra, the total peak areas A to D are calculated by the following procedures (1) to (4).
(1) 1780 cm connected by ^-1 and the linear absorbance 1493cm ^-1 (N), the area surrounded by the absorption spectra and N of the absorption band 1493Cm ^-1 or 1780 cm ^-1 or less in the range that the total peak area A.
(2) Draw a ^{straight line (O) vertically from the absorbance (Q) of 1690 cm -1} , let P be the intersection of N and O, and draw a straight line (S) vertically from the absorbance (R) of ^{1598 cm -1.} the intersection S is T, the absorption spectrum and the straight line S of the absorption band 1598cm ^-1 or 1690 cm ^-1 or less in the range, the point T, the straight line N, the point P, the straight line O, absorbance Q, the total peak area surrounded by absorbance R The area is B.
(3) the absorption spectrum and absorbance Q absorption bands 1690 cm ^-1 or 1780 cm ^-1 or less in the range, the linear O, a point P, and the area surrounded by straight lines N and total peak area C.
(4) Absorption band The ^{area surrounded by the absorption spectrum in the range of 1493 cm -1} or more and 1598 cm ^-1 or less and the absorbance R, the straight line S, the point T, and the straight line N is defined as the total peak area D.
Next, the area ratio (C / A), (B / A) and (D / A) are obtained from the area obtained by the above method.
In the present embodiment, the infrared absorption spectrum is measured (infrared total reflection measurement: ATR method) by using, for example, an IRT-5200 device manufactured by Nippon Spectroscopy Co., Ltd., and mounting a PKM-GE-S (Germanium) crystal. It can be performed under the conditions of an angle of 45 degrees, a room temperature, a resolution of 4 cm ^{-1, and an integration count of 100 times.}

The gas barrier polymer layer 103 formed of a mixture containing a polycarboxylic acid and a polyamine compound has two types of cross-linked structures, ion cross-linked and amide cross-linked, and the abundance ratio of these cross-linked structures improves gas barrier performance. It is important from the viewpoint. Here, the ionic cross-linking is generated by causing an acid-base reaction between a carboxyl group contained in a polycarboxylic acid and an amino group contained in a polyamine compound, and the amide cross-linking is a polycarboxylic acid. It is produced by causing a dehydration condensation reaction between the contained carboxyl group and the amino group contained in the polyamine compound.

In the gas barrier laminate 100, in addition to the selection of the material of the gas barrier polymer layer 103 and the selection of the heating method, the heating temperature and the heating time at the time of forming the gas barrier polymer layer 103, in the gas barrier polymer layer 103 ( By configuring the area ratio of the amide bond represented by B / A) to be within a specific range, the oxygen barrier property after the retort treatment and the bending (gerbo) treatment can be further improved. ..
The reason why such a gas barrier laminate 100 is excellent in oxygen barrier properties after retort treatment and bending (gerbo) treatment is not necessarily clear, but it is a dense and strong film due to the amide bond formed in the gas barrier polymer layer. It is presumed that it can be made into a structure.

Further, the gas barrier polymer layer 103 in which the area ratio of the amide bond represented by (B / A) is in a specific range appropriately adjusts the production conditions of the gas barrier polymer constituting the gas barrier polymer layer 103. Can be obtained by More specifically, the types of polycarboxylic acids and polyamine compounds which are raw materials for gas barrier polymers, their blending ratios, methods for preparing gas barrier coating materials, methods and conditions for heat treatment of gas barrier coating materials, and the like are described. It is mentioned as a factor for controlling the area ratio of the above (B / A).

In the infrared absorption spectrum of the gas barrier polymer layer 103, the area ratio of the amide bond represented by (B / A) is preferably 0 from the viewpoint of improving the gelbo resistance and maintaining the oxygen barrier property after the retort treatment. .225 or more, more preferably 0.235 or more, still more preferably 0.245 or more.
The area ratio (B / A) is preferably 0.460 or less, more preferably 0.400 or less, still more preferably 0.395 or less, still more preferably 0.395 or less, from the viewpoint of maintaining gelbo resistance and the like. Is 0.390 or less.

Further, in the infrared absorption spectrum of the gas barrier polymer layer 103, the area ratio of the carboxylic acid represented by (C / A) is preferably 0.150 or more, more preferably 0.150 or more, from the viewpoint of appearance and dimensional stability. It is 0.155 or more, more preferably 0.160 or more, and even more preferably 0.165 or more.
The area ratio (C / A) is preferably 0.280 or less, more preferably 0.275 or less, still more preferably 0.270 or less, from the viewpoint of improving gelbo resistance and oxygen barrier property. Is.

In the infrared absorption spectrum of the gas barrier polymer layer 103, the area ratio of the carboxylate represented by (D / A) is preferably 0. It is 300 or more, more preferably 0.310 or more, still more preferably 0.315 or more.
The area ratio (D / A) is preferably 0.600 or less, more preferably 0.585 or less, still more preferably 0.580 or less, from the viewpoint of preventing deterioration of gelbo resistance and the like.

The thickness of the gas barrier polymer layer 103, here the thickness of the amide crosslinked membrane layer, is preferably 0.01 μm or more, more preferably 0.1 μm or more, from the viewpoint of improving the gas barrier property.
Further, from the viewpoint of obtaining stable adhesion to the base material layer 101, the thickness of the gas barrier polymer layer 103 is preferably 0.45 μm or less, more preferably 0.4 μm or less.

Next, an example of a method for producing the gas barrier polymer layer 103 will be described.
In the present embodiment, when the gas barrier polymer layer 103 is a layer obtained by heat-curing a mixture containing a polycarboxylic acid and a polyamine compound, the method for producing the gas barrier polymer layer 103 includes, for example, the following steps.
(Step 1) A step of applying a mixture containing a polycarboxylic acid and a polyamine compound to the inorganic layer 102 provided on the base material layer 101 to obtain a coated layer.
(Step 2) A step of forming a gas barrier polymer layer 103 having an amide bond by heating a coating layer and causing a dehydration condensation reaction between a carboxyl group contained in a polycarboxylic acid and an amino group contained in a polyamine compound. ..
Hereinafter, steps 1 and 2 will be described in more detail.

(Step 1)
Step 1 is a step of coating the inorganic layer 102 on the base material layer 101 with a mixture containing a polycarboxylic acid and a polyamine compound to obtain a coated layer.
First, the polycarboxylic acid and the polyamine compound constituting the above mixture, that is, the coating material for the gas barrier will be described.

(Polycarboxylic acid)
In this embodiment, the polycarboxylic acid has two or more carboxy groups in the molecule. Specifically, homopolymers of α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, cinnamic acid, 3-hexenoic acid, and 3-hexendioic acid, or homopolymers thereof. Examples include copolymers. Further, it may be a copolymer of the above α, β-unsaturated carboxylic acid with esters such as ethyl esters and olefins such as ethylene.
Among these, homopolymers of acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, and cinnamic acid or copolymers thereof are preferable, and polyacrylic acid (PAA), polymethacrylic acid, acrylic acid and methacrylic acid are preferable. It is more preferable that it is one kind or two or more kinds of polymers selected from the copolymer with, and it is further preferable that it is at least one kind of polymer selected from polyacrylic acid and polymethacrylic acid. It is even more preferable that the polymer is at least one selected from a homopolymer and a methacrylic acid homopolymer.
Here, in the present embodiment, the polyacrylic acid includes both a homopolymer of acrylic acid and a copolymer of acrylic acid and other monomers. In the case of a copolymer of acrylic acid and other monomers, polyacrylic acid contains a structural unit derived from acrylic acid in 100% by mass of the polymer, usually 90% by mass or more, preferably 95% by mass or more. It preferably contains 99% by mass or more.
Further, in the present embodiment, the polymethacrylic acid includes both a homopolymer of methacrylic acid and a copolymer of methacrylic acid and another monomer. In the case of a copolymer of methacrylic acid and another monomer, polymethacrylic acid contains a constituent unit derived from methacrylic acid in 100% by mass of the polymer, usually 90% by mass or more, preferably 95% by mass or more. It preferably contains 99% by mass or more.

In the present embodiment, the polycarboxylic acid is a polymer obtained by polymerizing a carboxylic acid monomer. The molecular weight of the polycarboxylic acid is preferably 5 × 10 ² or more, more preferably 1.5 × 10 ³ or more, still more preferably 5 × 10 ³ or more, and more, from the viewpoint of excellent balance between gas barrier property and handleability. More preferably 7 × 10 ³ or more, further preferably 1 × 10 ⁴ or more, particularly preferably 5 × 10 ⁴ or more, still preferably 2 × 10 ⁶ or less, more preferably 1 × 10 ⁶ or less, more preferably 5 × 10 ⁵ or less, more preferably 2.5 × 10 ⁵ or less, furthermore preferably 2 × 10 ⁵ or less, especially preferably 1.5 × 10 ⁵ or less.
Here, in the present embodiment, the molecular weight of the polycarboxylic acid is a weight average molecular weight in terms of polyethylene oxide, and can be measured by gel permeation chromatography (GPC).

(Polyamine compound)
In this embodiment, the polyamine compound is a polymer having two or more amino groups at the main chain, side chain, or terminal. Specific examples of the polyamine compound include aliphatic polyamines such as polyallylamine, polyvinylamine, polyethyleneimine (PEI), and poly (trimethylethyleneimine); polyamides having an amino group in the side chain such as polylysine and polyarginine. Kind; etc. Further, the polyamine compound may be a polyamine in which a part of the amino group is modified. From the viewpoint of obtaining good gas barrier properties, the polyamine compound is preferably polyethyleneimine.

The weight average molecular weight of the polyamine compound is preferably 5 × 10 ¹ or more, more preferably 1 × 10 ² or more, still more preferably 1.5 × 10 ³ or more, from the viewpoint of excellent balance between gas barrier properties and handleability. It is even more preferably 3.5 × 10 ³ or more, further preferably 5 × 10 ³ or more, particularly preferably 7 × 10 ³ or more, and preferably 5 × 10 ⁶ or less, more preferably 2 × 10 ⁶ or less, more preferably 1 × 10 ⁶ or less, even more preferably 5 × 10 ⁵ or less, still more preferably 1 × 10 ⁵ or less, still more preferably 7 × 10 ⁴ or less, still more preferably 5 × 10 ⁴ Below, it is more preferably 3 × 10 ⁴ or less, and particularly preferably 1.5 × 10 ⁴ or less.
Here, in the present embodiment, the molecular weight of the polyamine compound can be measured by using a boiling point elevation method or a viscosity method.

(Mixing ratio of polycarboxylic acid and polyamine compound)
In this embodiment
((Number of moles of -COO- group contained in polycarboxylic acid in gas barrier coating material) / (Number of moles of amino group contained in polyamine compound in gas barrier coating material)) is a gas barrier polymer layer 103. From the viewpoint of improving the gas barrier property and productivity of the above, it is preferably 100/40 or less, more preferably 100/45 or less, and further preferably 100/50 or less.
From the same viewpoint, ((number of moles of -COO- group contained in polycarboxylic acid in gas barrier coating material) / (number of moles of amino group contained in polyamine compound in gas barrier coating material)) is It is preferably 100/70 or more, preferably 100/65 or more, and more preferably 100/60 or more.

Next, a method for preparing a coating material for a gas barrier in step 1 will be described. The coating material for a gas barrier can be obtained, for example, as follows.
First, the carboxy group of the polycarboxylic acid is completely or partially neutralized by adding a base to the polycarboxylic acid. The polyamine compound is then added to the polycarboxylic acid with the carboxy group completely or partially neutralized. By mixing the polycarboxylic acid and the polyamine compound in such a procedure, the formation of aggregates of the polycarboxylic acid and the polyamine compound can be suppressed, and a uniform gas barrier coating material can be obtained. This makes it possible to more effectively proceed with the dehydration condensation reaction between the -COO- group contained in the polycarboxylic acid and the amino group contained in the polyamine compound.

Here, by neutralizing the polycarboxylic acid with a base, it is possible to suppress the occurrence of gelation when the polyamine compound and the polycarboxylic acid are mixed. Therefore, in the polycarboxylic acid, it is preferable to use a base to make a partially neutralized product or a completely neutralized product of a carboxy group from the viewpoint of preventing gelation. The neutralized product can be obtained by partially or completely neutralizing the carboxy group of the polycarboxylic acid with a base, that is, by partially or completely converting the carboxy group of the polycarboxylic acid into a carboxylate. can. This makes it possible to prevent gelation when the polyamine compound is added.
The partially neutralized product is prepared by adding a base to an aqueous solution of the polycarboxylic acid, and the desired degree of neutralization can be obtained by adjusting the amount ratio of the polycarboxylic acid to the base. In the present embodiment, the degree of neutralization of the polycarboxylic acid with the base is preferably 30 to 100 equivalent% from the viewpoint of sufficiently suppressing gelation due to the neutralization reaction with the amino group of the polyamine compound. It is preferably 40 to 100 equivalent%, more preferably 50 to 100 equivalent%.

As the base, any water-soluble base can be used. As the water-soluble base, either or both of a volatile base and a non-volatile base can be used, but the volatility is easy to remove during drying and curing from the viewpoint of suppressing the deterioration of the gas barrier property due to the remaining free base. It is preferably a base.
Examples of the volatile base include tertiary amines such as ammonia, morpholine, alkylamine, 2-dimethylaminoethanol, N-methylmonophorin, ethylenediamine, and triethylamine, aqueous solutions thereof, or mixtures thereof. An aqueous ammonia solution is preferable from the viewpoint of obtaining good gas barrier properties.
Examples of the non-volatile base include sodium hydroxide, lithium hydroxide, potassium hydroxide, an aqueous solution thereof, or a mixture thereof.

Further, the solid content concentration of the gas barrier coating material is preferably set to 0.5 to 15% by mass, more preferably 1 to 10% by mass, from the viewpoint of improving the coatability.

Further, it is preferable to further add a surfactant to the coating material for the gas barrier from the viewpoint of preventing the generation of cissing during coating. The amount of the surfactant added is preferably 0.01 to 3% by mass, more preferably 0.01 to 1% by mass, when the total solid content of the gas barrier coating material is 100% by mass.

In the present embodiment, examples of the surfactant include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and the like, from the viewpoint of obtaining good coatability. Therefore, nonionic surfactants are preferable, and polyoxyethylene alkyl ethers are more preferable.

Examples of the nonionic surfactant include polyoxyalkylene alkylaryl ethers, polyoxyalkylene alkyl ethers, polyoxyalkylene fatty acid esters, sorbitan fatty acid esters, silicone-based surfactants, and acetylene alcohol-based surfactants. , Fluorine-containing surfactant and the like.

Examples of the polyoxyalkylene alkyl aryl ethers include polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, and polyoxyethylene dodecylphenyl ether.
Examples of the polyoxyalkylene alkyl ethers include polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether and polyoxyethylene lauryl ether.
Examples of the polyoxyalkylene fatty acid ester include polyoxyethylene oleic acid ester, polyoxyethylene lauric acid ester, and polyoxyethylene distearate.
Examples of the sorbitan fatty acid esters include sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquiorate, polyoxyethylene monooleate, and polyoxyethylene stearate.
Examples of the silicone-based surfactant include dimethylpolysiloxane and the like.
Examples of the acetylene alcohol-based surfactant include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3, 5-Dimethyl-1-hexyne-3ol and the like can be mentioned.
Examples of the fluorine-containing surfactant include a fluorine alkyl ester and the like.

Further, the coating material for a gas barrier may contain other additives as long as the object of the present invention is not impaired. For example, various additives such as lubricants, slip agents, anti-blocking agents, antistatic agents, antistatic agents, pigments, dyes, inorganic or organic fillers, and polyvalent metal compounds may be added.

Next, a coating material for a gas barrier is applied to the base material layer 101 to obtain a coating layer.
The method of applying the gas barrier coating material to the base material layer 101 is not limited, and a usual method can be used. For example, Mayer bar coater, air knife coater, direct gravure coater, gravure offset, arc gravure coater, gravure coater such as gravure reverse and jet nozzle method, top feed reverse coater, bottom feed reverse coater and reverse roll such as nozzle feed reverse coater. Examples thereof include a method of coating using various known coating machines such as a coater, a 5-roll coater, a lip coater, a bar coater, a bar reverse coater, a die coater, and an applicator.

The thickness (wet thickness) of the coating layer is preferably 0.05 μm or more, more preferably 1 μm or more, from the viewpoint of improving the barrier performance of the obtained gas barrier laminate 100.
Further, from the viewpoint of suppressing curling of the obtained gas barrier laminate 100, and from the viewpoint of more effectively promoting the dehydration condensation reaction between the -COO- group contained in the polycarboxylic acid and the amino group contained in the polyamine compound. Therefore, the wet thickness is preferably 300 μm or less, more preferably 200 μm or less, still more preferably 100 μm or less, and even more preferably 30 μm or less.
Further, specific examples of the thickness of the gas barrier polymer layer 103 after the heat treatment are as described above.

(Step 2)
Step 2 is a step of forming a gas barrier polymer layer having an amide bond by heating the coating layer and causing a dehydration condensation reaction between the carboxyl group contained in the polycarboxylic acid and the amino group contained in the polyamine compound. be.
By adopting the heat treatment method, temperature, and time at this time, each factor such as the amount of coating material for gas barrier, the type of equipment used for heat treatment, heat treatment temperature, and heat treatment time is highly controlled. It is important to combine them. For example, a coating material for a gas barrier is applied to the side of the inorganic material layer 102 of the base material layer 101 so that the wet thickness is 0.05 to 300 μm, and the material is heated and dried by a known device used for heat treatment.
The method of drying and heat treatment is not limited as long as the gas barrier polymer layer 103 in the present embodiment can be formed, but any method may be used as long as it can cure the gas barrier coating material or heat the cured gas barrier coating material.
Specific examples of the heating means include convection heat transfer such as a hot air dryer, hot air oven, and dryer, conduction heat transfer such as a heating roll, and radiant heat transfer using electromagnetic waves such as infrared, far-infrared / near-infrared heaters. This includes those caused by internal heat generation such as microwaves.
As the device used for drying and heat treatment, a device capable of both drying and heat treatment is preferable from the viewpoint of manufacturing efficiency. Among them, specifically, it is preferable to use a hot air oven from the viewpoint that it can be used for various purposes such as drying, heating, and annealing, and from the viewpoint of excellent heat conduction efficiency to the film, a heating roll is used. Is preferable. Further, the methods used for drying and heat treatment may be appropriately combined. A hot air oven and a heating roll may be used in combination. For example, if the coating material for a gas barrier is dried in the hot air oven and then heat-treated with the heating roll, the heat treatment step becomes short and it is preferable from the viewpoint of production efficiency. Further, it is preferable to perform drying and heat treatment only in a hot air oven.

When the gas barrier coating material is dried using a hot air oven, it is preferably treated at a heating temperature of 140 to 250 ° C. for 1 second to 5 minutes, and more preferably at a heating temperature of 180 to 240 ° C. for 5 seconds to 3 minutes. Then, more preferably, the heat treatment is performed at a heating temperature of 200 to 230 ° C. for 15 seconds to 3 minutes.
From the viewpoint of effectively advancing the dehydration condensation reaction between the -COO- group contained in the polycarboxylic acid and the amino group contained in the polyamine compound, the heat treatment temperature and the heat treatment time depend on the wet thickness of the coating material for the gas barrier. It is important to adjust.

In step 2, the coating layer may be dried before the heating of the coating layer. The above drying and heat treatment may be performed at the same time.
When drying is performed before the heat treatment of the coating layer in step 2, it is desirable to perform drying under the conditions of a drying temperature of 60 to 150 ° C. and a drying time of 1 second to 60 seconds.

The gas barrier polymer layer 103 is obtained by the above procedure. Further, the gas barrier polymer layer 103 is formed by the above-mentioned gas barrier coating material, and after the gas barrier coating material is applied to the inorganic layer 102, it is dried and heat-treated to cure the gas barrier coating material. It is obtained by doing so.

In the present embodiment, the oxygen permeability of the gas barrier polymer layer 103 at a thickness of 1 μm at 20 ± 2 ° C. and 90 ± 5% RH is preferably 45 mL / (m ² · day) from the viewpoint of obtaining good gas barrier properties. -MPa) or less, more preferably 40 mL / (m ² · day · MPa) or less. Although the lower limit of the oxygen permeability is ^{0mL / (m 2 · day ·} MPa), it may be e.g. ^{1mL / (m 2 · day ·} MPa) or higher.
The oxygen permeability is measured according to JIS K 7126 under the conditions of a temperature of 20 ± 2 ° C. and a humidity of 90 ± 5% RH.

(Inorganic layer)
In the present embodiment, it is preferable that the inorganic layer 102 is provided between the base material layer 101 of the gas barrier laminate 100 and the gas barrier polymer layer 103 from the viewpoint of improving the gas barrier property. By providing the inorganic layer 102, in combination with the structure of the gas barrier polymer layer 103, even more excellent bending resistance and gas barrier property after retort treatment can be obtained. Further, since the inorganic layer 102 and the gas barrier polymer layer 103 having an amide crosslink are excellent in adhesiveness between the layers, the gas barrier polymer layer 103 has stable adhesion against external deformation to the gas barrier laminate 100. You can keep the state.

Examples of the inorganic substance constituting the inorganic substance layer 102 include metals, metal oxides, metal nitrides, metal fluorides, metal oxynitrides and the like capable of forming a thin film having a barrier property.
Examples of the inorganic substances constituting the inorganic substance layer 102 include periodic table group 2A elements such as beryllium, magnesium, calcium, strontium, and barium; periodic table transition elements such as titanium, zirconium, ruthenium, hafnium, and tantalum; periodic table of zinc and the like. Group 2B elements; Periodic table of group 3A elements such as aluminum, gallium, indium, and tarium; Periodic table of group 4A elements such as silicon, germanium, and tin; Periodic table of group 6A elements such as selenium, tellurium, etc. One or more selected from a substance, a fluoride, an oxynitride and the like can be mentioned.
In this embodiment, the family name of the periodic table is shown by the old CAS formula.

Further, among the above-mentioned inorganic substances, one or more kinds of inorganic substances selected from the group consisting of silicon oxide, aluminum oxide and aluminum are preferable because they are excellent in balance of barrier property, cost and the like, and the inorganic substance is aluminum oxide. It is more preferable to have.
In addition to silicon dioxide, silicon monoxide and silicon suboxide may be contained in the silicon oxide.

The inorganic substance layer 102 is composed of the above-mentioned inorganic substances. The inorganic layer 102 may be composed of a single inorganic layer or may be composed of a plurality of inorganic layers. When the inorganic layer 102 is composed of a plurality of inorganic layers, it may be composed of the same type of inorganic layer or may be composed of different types of inorganic layers.

When the inorganic layer 102 is an aluminum oxide layer made of aluminum oxide, Kα rays of aluminum obtained by fluorescent X-ray analysis of the aluminum oxide layer from the viewpoint of stable adhesion of the aluminum oxide layer. The Kα ray intensity of the aluminum obtained by fluorescent X-ray analysis of an aluminum layer having an intensity of P (kcps), made of aluminum, and obtained under the same manufacturing conditions as the aluminum oxide layer except that oxygen is not introduced. When Q (kcps), the adhesion rate defined by (P / Q) is preferably 0.50 or more and 0.75 or less, more preferably 0.52 or more and 0.70 or less, and further preferably 0.53. It is 0.65 or more, more preferably 0.55 or more and 0.60 or less. By setting the adhesion rate within the above range, it is possible to obtain the gas barrier laminate 100 in which the gas barrier polymer layer 103 can maintain a more stable adhesive state against external deformation.

The Kα ray intensity P can be obtained by, for example, the following method.
Using a fluorescent X-ray analyzer ZSXPrimusII (manufactured by Rigaku Co., Ltd.), Kα rays of aluminum constituting the aluminum oxide layer were measured with respect to the aluminum oxide layer of the gas barrier laminate 100 of the present embodiment, and the obtained fluorescence was obtained. The X-ray intensity can be Kα-ray intensity P (kcps).
The Kα ray intensity Q is obtained, for example, by the following method.
First, an aluminum layer made of aluminum is formed on the base material layer under the same manufacturing conditions as the aluminum oxide layer in the gas barrier laminate 100 of the present embodiment without introducing oxygen. Next, using the fluorescent X-ray analyzer ZSXPrimusII (manufactured by Rigaku), the Kα rays of the aluminum constituting the aluminum layer were measured with respect to the obtained aluminum layer, and the obtained fluorescent X-ray intensity was Q (kcps). ).

Here, the Kα-ray intensity P of the obtained aluminum oxide layer depends on the amount of oxygen introduced, and as the amount of oxygen introduced (degree of oxidation) increases, the amount of vapor deposition as aluminum decreases, so the Kα-ray intensity P is small. Therefore, if the amount of oxygen introduced is small, the amount of vapor deposition as aluminum increases, so that the Kα ray intensity P increases.

Further, in the gas barrier laminated body 100 of the present embodiment, when the inorganic material layer 102 is a metal oxide layer composed of a metal oxide, the metal obtained by fluorescent X-ray analysis of the metal oxide layer. A metal layer is obtained under the same manufacturing conditions as the above-mentioned metal oxide layer except that the Kα-ray intensity of the metal constituting the oxide is R (kcps), the metal is composed of the metal constituting the metal oxide, and oxygen is not introduced. When the Kα ray intensity of the metal obtained by fluorescent X-ray analysis is S (kcps), the adhesion rate defined by (R / S) is preferably 0.50 or more and 0.90 or less, more preferably. Is 0.55 or more and 0.80 or less. When the adhesion rate is within the above range, the gas barrier laminate 100 having an excellent balance between gas barrier property and transparency can be obtained.
Here, the Kα ray intensities R and S can be measured by the same method as the Kα ray intensities P and Q.

The thickness of the inorganic layer 102 is usually 1 nm or more and 1000 nm or less, preferably 1 nm or more and 500 nm or less, more preferably 1 nm or more and 100 nm or less, and further preferably 1 nm or more and 50 nm from the viewpoint of the balance of barrier property, adhesion, handleability and the like. Below, it is even more preferably 1 nm or more and 20 nm or less.
In the present embodiment, the thickness of the inorganic layer 102 can be determined from an observation image by a transmission electron microscope or a scanning electron microscope.

The method for forming the inorganic layer 102 is not limited, and for example, a vacuum vapor deposition method, an ion plating method, a sputtering method, a chemical vapor deposition method, a physical vapor deposition method, a chemical vapor deposition method (CVD method), and a plasma CVD method. , The inorganic layer 102 can be formed on one side or both sides of the base material layer 101 by the solgel method or the like. Above all, film formation under reduced pressure such as a sputtering method, an ion plating method, a chemical vapor deposition method (CVD), a physical vapor deposition method (PVD), or a plasma CVD method is desirable. As a result, chemically active molecular species containing silicon such as silicon nitride and silicon oxide react rapidly, thereby improving the smoothness of the surface of the inorganic layer 102 and reducing the number of pores. It is expected to be.
In order to carry out these bonding reactions rapidly, it is desirable that the inorganic atom or compound is a chemically active molecular species or atomic species.

(Base layer)
The base material layer 101 is formed of, for example, a thermosetting resin, a thermoplastic resin, or an organic material such as paper, and preferably contains at least one selected from a thermosetting resin and a thermoplastic resin.

Examples of the thermosetting resin include known thermosetting resins such as epoxy resin, unsaturated polyester resin, phenol resin, urea-melamine resin, polyurethane resin, silicone resin, and polyimide.

Examples of the thermoplastic resin include known thermoplastic resins such as polyolefins (polyethylene, polypropylene, poly (4-methyl-1-pentene), poly (1-butene), etc.) and polyesters (polyethylene terephthalate, polybutylene terephthalate, polyethylene). Naphthalate, etc.), Polyamide (nylon-6, nylon-66, polymethoxylen adipamide, etc.), polyvinyl chloride, polyimide, ethylene vinyl acetate copolymer or its saponified product, polyvinyl alcohol, polyacrylonitrile, polycarbonate, polystyrene, etc. , Ionomer, fluororesin or a mixture thereof and the like.
Among these, from the viewpoint of improving transparency, one or more selected from polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyamide, and polyimide is preferable, and polyethylene terephthalate and polyethylene naphthalate are selected. One or more of them are more preferable.
Further, the base material layer 101 formed of the thermoplastic resin may be a single layer or two or more types of layers depending on the use of the gas barrier laminate 100.

Further, the film formed of the thermosetting resin and the thermoplastic resin may be stretched in at least one direction, preferably biaxially, to form the base material layer 101.

The base material layer 101 is formed of one or more thermoplastic resins selected from polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyamide, and polyimide from the viewpoint of excellent transparency, rigidity, and heat resistance. The biaxially stretched film is preferable, and the biaxially stretched film formed of one or more kinds of thermoplastic resins selected from polyethylene terephthalate and polyethylene naphthalate is more preferable.

Further, the surface of the base material layer 101 may be coated with polyvinylidene chloride, polyvinyl alcohol, an ethylene / vinyl alcohol copolymer, an acrylic resin, a urethane resin, or the like.
Further, in order to improve the adhesiveness with the gas barrier polymer layer 103, the base material layer 101 may be surface-treated. Specifically, surface activation treatments such as corona treatment, flame treatment, plasma treatment, and primer coating treatment may be performed.

The thickness of the base material layer 101 is preferably 1 to 1000 μm, more preferably 1 to 500 μm, and even more preferably 1 to 300 μm from the viewpoint of obtaining good film characteristics.

The shape of the base material layer 101 is not limited, and examples thereof include a sheet or film shape, a tray, a cup, and a hollow body.

The gas barrier laminate 100 includes the base layer 101, the inorganic layer 102, and the gas barrier polymer layer 103.
In the present embodiment, the oxygen permeability of the entire gas barrier laminate 100 after retort treatment at 130 ° C. for 30 minutes with a high temperature and high pressure retort sterilizer is preferably 200 mL / from the viewpoint of obtaining good gas barrier properties. (M ² · day · MPa) or less, more preferably 150 mL / (m ² · day · MPa) or less, still more preferably 120 mL / (m ² · day · MPa) or less, still more preferably 100 mL / (m ² · MPa) or less. day · MPa) or less.

Further, the gas barrier laminate 100 may include a layer other than the base material layer 101, the inorganic layer 102 and the gas barrier polymer layer 103. Specific examples of other layers include an undercoat layer and an adhesive layer.

(Undercoat layer)
In the gas barrier laminate 100, an undercoat layer may be further laminated on the substrate layer 101 from the viewpoint of improving the adhesiveness between the substrate layer 101 and the gas barrier polymer layer 103 or the inorganic layer 102. .. By providing an undercoat layer between the base material layer 101 and the gas barrier polymer layer 103 or the inorganic layer 102, the followability of the gas barrier polymer layer 103 is further improved and the gas barrier is further subjected to external deformation. In the sex laminate 100, the gas barrier polymer layer 103 can maintain a more stable adhesive state.
The undercoat layer is preferably composed of, for example, one or more selected from polyurethane-based resin, polyester-based resin, oxazoline-based resin, and acrylic-based resin.

The thickness of the undercoat layer is preferably 0.001 μm or more from the viewpoint of obtaining good adhesiveness, and preferably 0.5 μm or less from the viewpoint of economic efficiency. It is more preferably 0.005 to 0.1 μm, and even more preferably 0.01 to 0.05 μm.

Further, an adhesive layer may be provided between the base material layer 101 and the gas barrier polymer layer 103. The undercoat layer is removed from the adhesive layer below.
The adhesive layer may be one containing a known adhesive. The adhesive is composed of an organic titanium resin, a polyethyleneimine resin, a urethane resin, an epoxy resin, an acrylic resin, a polyester resin, an oxazoline group-containing resin, a modified silicone resin and an alkyl titanate, a polyester polybutadiene, and the like. Examples thereof include one-component and two-component polyols and polyvalent isocyanates, water-based urethanes, and ionomers. Alternatively, an aqueous adhesive containing an acrylic resin, a vinyl acetate resin, a urethane resin, a polyester resin or the like as a main raw material may be used.
Further, other additives such as a curing agent and a silane coupling agent may be added to the adhesive depending on the use of the gas barrier laminate. When the gas barrier laminated body is used for hot water treatment such as retort, a dry laminating adhesive typified by a polyurethane adhesive is preferable from the viewpoint of heat resistance and water resistance, and a solvent-based adhesive is preferable. A two-component curing type polyurethane adhesive is more preferable.

The gas barrier laminated body 100 of the present embodiment is excellent in gas barrier performance, and is a package containing various packages, particularly food packages having contents that require high gas barrier properties, and the gas barrier laminated body of the present embodiment. Not only enables long-term storage of the contents, but also has excellent durability against the load of deformation force in the process of forming the package, that is, gelbo resistance, and functions such as oxygen barrier property even after retort treatment. It is unlikely to drop. Therefore, the package of the present embodiment can be applied not only to various contents but also to various processing methods such as squeezing processing and retort processing that require durability against the load of deforming force. It can also be suitably used as a packaging body for various purposes such as medical use such as an infusion bag, industrial use, and daily miscellaneous goods use.
Further, the package in the present embodiment includes the gas barrier laminate 100.
Further, since the gas barrier laminate 100 of the present embodiment has excellent durability against a load of deformation force, that is, gelbo resistance and the oxygen barrier property and the like are unlikely to decrease, for example, a load of deformation force is applied to the film. Even after that, it can be suitably used as a vacuum heat insulating film; a sealing film for sealing an electroluminescence element, a solar cell, or the like; which requires a high barrier performance for the film.

Although the embodiments of the present invention have been described above with reference to the drawings, these are examples of the present invention, and various configurations other than the above can be adopted.
Hereinafter, an example of the reference form will be added.
1. 1. With the base material layer,
A gas barrier polymer layer provided on at least one surface of the base material layer and
It is a gas barrier laminated body containing
A sample obtained by subjecting the gas barrier laminate to a gelbo treatment under the following condition 1 and then retort-treated under the following condition 2 and a sample obtained by retort-treating under the following condition 2. A gas barrier laminate having an oxygen permeability at 20 ± 2 ° C. and 90 ± 5% RH of 150 mL / (m ² · day · MPa) or less.
(Condition 1) Using a gelboflex tester (manufactured by Tester Sangyo Co., Ltd.), bending treatment was performed 10 times under the conditions of an atmospheric temperature of 23 ± 2 ° C. and 50 ± 5% RH.
(Condition 2) Retort treatment at 130 ° C for 30 minutes with a high-temperature and high-pressure retort sterilizer.
2. 2. 1. An inorganic layer is provided between the base material layer and the gas barrier polymer layer. The gas barrier laminate according to.
3. 3. 2. The inorganic layer is formed of one or more inorganic substances selected from the group consisting of silicon oxide, aluminum oxide and aluminum. The gas barrier laminate according to.
4. 1. The gas barrier polymer layer is formed by heat-curing a mixture containing a polycarboxylic acid and a polyamine compound. To 3. The gas barrier laminate according to any one.
5. In the infrared absorption spectrum of the gas barrier polymer layer,
The total peak area in the range of absorption band 1493 cm ^-1 or more and 1780 cm ^{-1 or less is defined as A.}
When the total peak area in the range of the absorption band 1598cm ^-1 or 1690 cm ^-1 and is B,
3. The area ratio of the amide bond represented by (B / A) is 0.400 or less. The gas barrier laminate according to.
6. In the infrared absorption spectrum of the gas barrier polymer layer,
When the total peak area in the range of the absorption band 1690 cm ^-1 or 1780 cm ^-1 and as C,
3. The area ratio of the carboxylic acid represented by (C / A) is 0.150 or more and 0.280 or less. Or 5. The gas barrier laminate according to.
7. In the infrared absorption spectrum of the gas barrier polymer layer,
When the total peak area in the range of the absorption band 1493cm ^-1 or 1598cm ^-1 to as D,
3. The area ratio of the carboxylate represented by (D / A) is 0.300 or more and 0.600 or less. ~ 6. The gas barrier laminate according to any one.
8. ((Number of moles of -COO- group contained in the polycarboxylic acid in the mixture) / (Number of moles of amino group contained in the polyamine compound in the mixture)) is 100/70 or more and 100/40 or less. 4. ~ 7. The gas barrier laminate according to any one.
9. 4. The polycarboxylic acid comprises one or more polymers selected from the group consisting of polyacrylic acid, polymethacrylic acid, and copolymers of acrylic acid and methacrylic acid. ~ 8. The gas barrier laminate according to any one.
10. 4. The polyamine compound contains polyethyleneimine. ~ 9. The gas barrier laminate according to any one.
11. 1. The thickness of the gas barrier polymer layer is 0.01 μm or more and 0.45 μm or less. ~ 10. The gas barrier laminate according to any one.
12. 1. 1. ~ 11. A package containing the gas barrier laminate according to any one of the above.

Hereinafter, this embodiment will be described in detail with reference to Examples and Comparative Examples. The present embodiment is not limited to the description of these examples.

(Preparation of solution (Z))
Purified water was added to a mixture of ammonium polyacrylate (manufactured by Toagosei Co., Ltd., product name: Aron A-30, 30% aqueous solution, molecular weight: 1 × 10 ⁵ ) to obtain a 10% aqueous solution of ammonium polyacrylate. rice field.
(Preparation of solution (Y))
Purified water was added to polyethyleneimine (manufactured by Wako Pure Chemical Industries, Ltd., product name: polyethyleneimine, average molecular weight: about 1 × 10 ⁴ ) to obtain a 10% aqueous solution of polyethyleneimine.

(Example 1)
Using a 12 μm thick biaxially stretched polyethylene terephthalate film (PET12 manufactured by Unitika Ltd.) as a base material, aluminum is heated and evaporated on the corona-treated surface by a high-frequency induction heating method, and vapor deposition is performed while introducing oxygen. Then, an aluminum oxide film having a thickness of 8 nm was formed. As a result, an aluminum oxide-deposited PET film was obtained.

On the other hand, 87.5 g of the aqueous ammonium polyacrylate solution (Z) and 12.5 g of the aqueous polyethyleneimine solution (Y) were mixed and stirred to prepare a mixed solution.
Further, purified water was added so that the solid content concentration of the above mixed solution was 2.5% by mass, and after stirring until a uniform solution was obtained, a nonionic surfactant (polyoxyethylene lauryl ether, manufactured by Kao Co., Ltd.) was added. , Trade name: Emargen 120) was mixed so as to be 0.3% by mass with respect to the solid content of the mixed solution, and a solution (V) was prepared.

The obtained solution (V) was applied to the vapor-deposited surface of the aluminum oxide-deposited PET film with an applicator so that the coating amount after drying was 0.3 μm, and 90 at 150 ° C. using a hot air dryer. By heat-treating for a second, a gas barrier laminated film was obtained.
With respect to the obtained gas barrier laminated film, a multilayer film for evaluation was prepared and evaluated by the method described later. The evaluation results are also shown in Table 1.

(Example 2)
A gas barrier laminated film was prepared and evaluated according to Example 1, except that the heat treatment conditions using a hot air dryer were set to 210 ° C. for 7 seconds.

(Example 3)
Using a 12 μm-thick biaxially stretched polyethylene terephthalate film (PET12 manufactured by Unitika Ltd.) as a base material, the obtained solution (V) was applied to the corona-treated surface without depositing aluminum oxide, and A gas barrier laminated film was prepared and evaluated according to Example 1, except that the heat treatment conditions using a hot air dryer were set to 210 ° C. for 81 seconds.

(Comparative Example 1)
A substrate made of a biaxially stretched polyethylene terephthalate film (PET12 manufactured by Unitika Ltd.) having a thickness of 12 μm was used as a gas barrier film, and a multilayer film for evaluation was prepared and evaluated according to Example 1.

(Comparative Example 2)
In Example 3, a gas barrier laminated film was prepared and evaluated according to Example 1, except that the heat treatment conditions by the hot air dryer were set to 210 ° C. for 54 seconds.

(Comparative Example 3)
In Example 3, a gas barrier laminated film was prepared and evaluated according to Example 1, except that the heat treatment conditions by the hot air dryer were set to 210 ° C. for 43 seconds.

(Comparative Example 4)
In Example 3, a gas barrier laminated film was prepared and evaluated according to Example 1, except that the heat treatment conditions by the hot air dryer were set to 210 ° C. for 26 seconds.

(Comparative Example 5)
In Example 3, a gas barrier laminated film was prepared and evaluated according to Example 1, except that the heat treatment conditions by the hot air dryer were set to 210 ° C. for 13 seconds.

(Comparative Example 6)
In Example 3, a gas barrier laminated film was prepared and evaluated according to Example 1, except that the heat treatment conditions by the hot air dryer were set to 210 ° C. for 6 seconds.

(Preparation of multilayer film for evaluation)
(1) An ester adhesive (polyester adhesive (trade name manufactured by Mitsui Chemicals Polyurethane Co., Ltd.)) on one side of an unstretched polypropylene film (manufactured by Mitsui Chemicals Tohcello Co., Ltd., trade name: TUX FCS) having a thickness of 50 μm. : Takelac A310): 12 parts by mass, isocyanate-based curing agent (trade name: Takenate A3 manufactured by Mitsui Chemicals Polypropylene Co., Ltd.): 1 part by mass and ethyl acetate: 7 parts by mass) were applied. After drying, the aluminum oxide vapor-deposited PET film obtained in Examples is bonded to the vapor-deposited surface side, and the amide cross-linked film laminated films obtained in Examples and Comparative Examples are bonded to the amide cross-linked film surface side (dry laminate). Film 1 (sample for measuring physical properties before retort) was obtained.

(2) Ester-based adhesive (polyurethane-based adhesive (Mitsui Chemicals, Inc. product name: Takelac A525S): 9 on one side of a 70 μm-thick unstretched polypropylene film (Mitsui Chemicals Tocello Co., Ltd. product name: RXC-22). A parts by mass, an isocyanate-based curing agent (trade name: Takenate A50 manufactured by Mitsui Chemicals, Inc.): 1 part by mass and ethyl acetate: 7.5 parts by mass) were applied. After drying, the aluminum oxide vapor-deposited PET film obtained in Examples is bonded to the vapor-deposited surface side, and the amide cross-linked film laminated films obtained in Examples and Comparative Examples are bonded to the amide cross-linked film surface side (dry laminate). Film 2 (sample for measuring physical properties after retort) was obtained.

(3) Gelbo (bending) treatment The multilayer film 1 or 2 obtained above is cut into a rectangle of 203 mm × 279 mm so that the unstretched polypropylene film is on the inner surface, and the back and front of the short side of the rectangle are 10 mm wide. After adhering them with double-sided tape to form a cylinder, fix both ends of the cylinder to the circular metal fittings of the Gelboflex tester (manufactured by Tester Sangyo). The attached tubular film was reciprocated 10 times at a speed of 40 times / min under the conditions of an atmospheric temperature of 23 ° C., a stroke of 152 mm and a twist of 440 degrees, and after gelbo treatment. A multilayer film was obtained.

(4) Retort treatment The multilayer film obtained in (2) or (3) above is folded back so that the unstretched polypropylene film is on the inner surface, heat-sealed on both sides to form a bag, and then water is added as the content. A bag was prepared by putting 70 cc in it and heat-sealing the other side, and this was retorted with a high-temperature and high-pressure retort sterilizer at 130 ° C. for 30 minutes. After the retort treatment, the contents were drained to obtain a multilayer film after the retort treatment.

(Evaluation method)
(IR area ratio)
The infrared absorption spectrum of the multilayer film obtained in (1) above was measured (infrared total reflection measurement: ATR method). Using an IRT-5200 device manufactured by JASCO Corporation, a PKM-GE-S (Germanium) crystal was attached, and measurements were taken under the conditions of an incident angle of 45 degrees, room temperature, a resolution of 4 cm-1, and an integration number of 100 times. The obtained absorption spectrum was analyzed by the method described above, and the total peak areas A to D were calculated. Then, the area ratios (B / A), (C / A), and (D / A) were obtained from the total peak areas A to D.

(Oxygen permeability [mL / (m ²・ day ・ MPa)])
The following four types of multilayer films were measured using OX-TRAN2 / 21 manufactured by Mocon Co., Ltd. under the conditions of temperature 20 ° C. and humidity 90% RH according to JIS K 7126.
(I) Multilayer film obtained in (1) above: Before gelbo, before retort (ii) Multilayer film obtained in (2) above retort-treated: Before gelbo, after retort (iii) Above (1) The multilayer film obtained in (1) was subjected to gelbo treatment: after gelbo and before retort (iv). The multilayer film obtained in (2) above was subjected to gelbo treatment and then retort treatment: after gelbo, after retort and retort treatment and gelbo. The processing conditions are as described in (4) and (3) above.

From Table 1, the gas barrier laminated film obtained in each example has an oxygen barrier property after the retort treatment and after the bending load, that is, after the bending (gerbo) treatment and the retort treatment. Was also excellent. Therefore, the gas barrier laminated film obtained in each example is suitably used for food packaging of contents that require high gas barrier property.

100 Gas barrier laminate 101 Base material layer 102 Inorganic layer 103 Gas barrier polymer layer

Claims (9)

With the base material layer,
A gas barrier polymer layer provided on at least one surface of the base material layer and
It is a gas barrier laminated body containing
The gas barrier polymer layer is formed by heat-curing a mixture containing a polycarboxylic acid and a polyamine compound.
In the infrared absorption spectrum of the gas barrier polymer layer,
The total peak area in the range of absorption band 1493 cm ^-1 or more and 1780 cm ^{-1 or less is defined as A.}
When the total peak area in the range of the absorption band 1598cm ^-1 or 1690 cm ^-1 and is B,
The area ratio of the amide bond represented by (B / A) is 0.400 or less, and the area ratio is 0.400 or less.
The thickness of the gas barrier polymer layer is 0.01 μm or more and 0.45 μm or less.
A sample obtained by subjecting the gas barrier laminate to a gelbo treatment under the following condition 1 and then retort-treated under the following condition 2 and a sample obtained by retort-treating under the following condition 2. A gas barrier laminate having an oxygen permeability at 20 ± 2 ° C. and 90 ± 5% RH of 150 mL / (m ² · day · MPa) or less.
(Condition 1) Using a gelboflex tester (manufactured by Tester Sangyo Co., Ltd.), bending treatment was performed 10 times under the conditions of an atmospheric temperature of 23 ± 2 ° C. and 50 ± 5% RH.
(Condition 2) Retort treatment at 130 ° C for 30 minutes with a high-temperature and high-pressure retort sterilizer. The gas barrier laminate according to claim 1, wherein an inorganic layer is provided between the substrate layer and the gas barrier polymer layer. The gas barrier laminate according to claim 2, wherein the inorganic layer is formed of one or more kinds of inorganic substances selected from the group consisting of silicon oxide, aluminum oxide and aluminum. In the infrared absorption spectrum of the gas barrier polymer layer,
When the total peak area in the range of the absorption band 1690 cm ^-1 or 1780 cm ^-1 and as C,
The gas barrier laminate according to any one of claims 1 to 3, wherein the area ratio of the carboxylic acid represented by (C / A) is 0.150 or more and 0.280 or less. In the infrared absorption spectrum of the gas barrier polymer layer,
When the total peak area in the range of the absorption band 1493cm ^-1 or 1598cm ^-1 to as D,
The gas barrier laminate according to any one of claims 1 to 4 , wherein the area ratio of the carboxylate represented by (D / A) is 0.300 or more and 0.600 or less. ((Number of moles of -COO- group contained in the polycarboxylic acid in the mixture) / (Number of moles of amino group contained in the polyamine compound in the mixture)) is 100/70 or more and 100/40 or less. The gas barrier laminate according to any one of claims 1 to 5. Any of claims 1 to 6 , wherein the polycarboxylic acid comprises one or more polymers selected from the group consisting of polyacrylic acid, polymethacrylic acid, and a copolymer of acrylic acid and methacrylic acid. The gas barrier laminate according to item 1. The gas barrier laminate according to any one of claims 1 to 7 , wherein the polyamine compound contains polyethyleneimine. A package containing the gas barrier laminate according to any one of claims 1 to 8.

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