JP7372147B2 - Gas barrier films and gas barrier laminates - Google Patents

Description

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

As a gas barrier material, a laminate in which an inorganic layer serving as a gas barrier layer is provided on a base layer is used.
However, this inorganic layer is weak against friction, etc., and such gas barrier laminates can suffer from cracks in the inorganic layer due to rubbing or stretching during post-processing, such as printing, lamination, or filling, and the gas barrier properties may deteriorate. It 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 including a gas barrier layer formed of a mixture containing a polycarboxylic acid and a polyamine compound is known.
Techniques related to such gas barrier laminates include, for example, Patent Document 1 (Japanese Patent Application Publication No. 2005-225940), Patent Document 2 (Japanese Patent Application Publication No. 2013-10857), and Patent Document 3 (International Publication No. 2016/017544). (No.).

Patent Document 1 discloses a gas barrier film having a gas barrier layer formed from a polycarboxylic acid, a polyamine and/or a polyol, and in which the degree of crosslinking of the polycarboxylic acid is 40% or more.
Patent Document 1 describes that such a gas barrier film has the same excellent gas barrier properties even under high humidity conditions as under low humidity conditions.

Patent Document 2 discloses that polyamine and polycarboxylic acid are coated on at least one side of a base material made of a plastic film so that the weight ratio of polyamine/polycarboxylic acid is 12.5/87.5 to 27.5/72.5. Disclosed is a film coated with a mixture comprising:
Patent Document 2 describes that such a gas barrier film has excellent gas barrier properties, particularly oxygen barrier properties, even after boiling, and is also excellent in flexibility, transparency, moisture resistance, chemical resistance, etc.

Patent Document 3 contains a polycarboxylic acid, a polyamine compound, a polyvalent metal compound, and a base, and the formula is (number of moles of -COO- groups contained in the polycarboxylic acid)/(number of moles of amino groups contained in the polyamine compound) )=100/20 to 100/90 is disclosed.
Patent Document 3 describes that when such a gas barrier coating material is used, a gas barrier film having good gas barrier properties, especially good oxygen barrier properties under both low humidity and high humidity conditions, and a laminate thereof. It is stated that it can provide.

JP2005-225940A Japanese Patent Application Publication No. 2013-10857 International Publication No. 2016/017544

The technical standards required for various properties of gas barrier materials are becoming higher and higher. The present inventors discovered the following problems with conventional gas barrier materials as described in Patent Documents 1 to 3.
Gas barrier materials such as those described in Patent Documents 1 to 3 require heating at high temperature for a long time in order to crosslink polycarboxylic acid and polyamine, so they are inferior in terms of productivity.
In addition, in order to improve productivity, such gas barrier materials can be formed by shortening the heat treatment time for crosslinking polycarboxylic acids and polyamines. It became clear that the ratio of amide bonds decreased and the barrier properties deteriorated.
Furthermore, according to studies by the present inventors, if a polyvalent metal compound is used instead of polyamine as a crosslinking agent for polycarboxylic acid, there is no need to crosslink polycarboxylic acid and polyamine, and the heat treatment time can be shortened. Although productivity can be improved, it has become clear that the interlayer adhesion of the resulting laminate becomes weaker and delamination is more likely to occur.
Thus, the present inventors have found that conventional gas barrier materials such as those described in Patent Documents 1 to 3 have an insufficient balance of barrier properties, delamination resistance, and productivity.
That is, the present inventors have found that there is room for improvement in conventional gas barrier materials from the viewpoint of improving barrier properties, delamination resistance, and productivity in a well-balanced manner.
Although many technologies have focused on improving barrier performance, no technology has been reported to date that improves barrier performance, delamination resistance, and productivity in a well-balanced manner.

The present invention has been made in view of the above circumstances, and provides a gas barrier material with an excellent balance of barrier properties, delamination resistance, and productivity.

The present inventors have conducted extensive research in order to achieve the above object. As a result, a gas barrier film composed of a cured product of a mixture containing polycarboxylic acid, a polyamine compound, and a polyvalent metal compound, and exhibiting a specific infrared absorption spectrum, has improved barrier properties, delamination resistance, and productivity. The present invention was completed based on the discovery that this product has excellent sexual balance.

That is, according to the present invention, the following gas barrier film and gas barrier laminate are provided.

[1]
A gas barrier film composed of a cured product of a mixture containing a polycarboxylic acid, a polyamine compound, and a polyvalent metal compound,
In the infrared absorption spectrum of the gas barrier film,
The total peak area in the absorption band range of 1493 cm ^-1 to 1780 cm ^-1 is A,
The total peak area in the absorption band 1598 cm ^-1 to 1690 cm ^-1 is defined as B,
The total peak area in the absorption band 1690 cm ^-1 to 1780 cm ^-1 is C,
When the total peak area in the absorption band 1493 cm ^-1 to 1598 cm ^-1 is D,
The area ratio of the amide bond represented by B/A is 0.380 or less,
The area ratio of carboxylic acid represented by C/A is 0.150 or less,
A gas barrier film having an area ratio of a carboxylic acid salt represented by D/A of 0.520 or more.
[2]
In the gas barrier film described in [1] above,
Gas barrier property where (number of moles of polyvalent metal derived from the polyvalent metal compound in the cured product)/(number of moles of -COO- group derived from the polycarboxylic acid in the cured product) is 0.16 or more film.
[3]
In the gas barrier film described in [1] or [2] above,
A gas barrier in which (number of moles of amino groups derived from the polyamine compound in the cured product)/(number of moles of -COO- groups derived from the polycarboxylic acid in the cured product) is 20/100 or more and 90/100 or less. sex film.
[4]
In the gas barrier film according to any one of [1] to [3] above,
A gas barrier film in which 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.
[5]
In the gas barrier film according to any one of [1] to [4] above,
A gas barrier film in which the polyvalent metal compound contains a divalent or higher valent metal compound.
[6]
In the gas barrier film according to any one of [1] to [5] above,
The polyvalent metal compound contains one or more divalent metal compounds selected from magnesium oxide, calcium oxide, barium oxide, zinc oxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, and zinc hydroxide. Gas barrier film.
[7]
In the gas barrier film according to any one of [1] to [6] above,
A gas barrier film in which the polyamine compound includes polyethyleneimine.
[8]
a base material layer;
A gas barrier layer provided on at least one surface of the base layer and composed of the gas barrier film according to any one of [1] to [7] above;
A gas barrier laminate comprising:
[9]
In the gas barrier laminate according to [8] above,
A gas barrier laminate in which the base layer contains one or more resins selected from the group consisting of polyamide, polyethylene terephthalate, and polybutylene terephthalate.
[10]
In the gas barrier laminate according to [8] or [9] above,
The base layer includes a first base layer and a second base layer,
The gas barrier layer, the first base layer, and the second base layer are laminated in this order, and the first base layer is made of a material selected from the group consisting of polyamide, polyethylene terephthalate, and polybutylene terephthalate. Or a gas barrier laminate containing two or more types of resin.
[11]
In the gas barrier laminate according to any one of [8] to [10] above,
A gas barrier laminate, wherein the gas barrier layer has a thickness of 0.01 μm or more and 15 μm or less.
[12]
In the gas barrier laminate according to any one of [8] to [11] above,
A gas barrier laminate further comprising an inorganic layer between the base layer and the gas barrier layer.
[13]
In the gas barrier laminate according to [12] above,
A gas barrier laminate, wherein the inorganic layer is formed of one or more inorganic materials selected from the group consisting of silicon oxide, aluminum oxide, and aluminum.
[14]
In the gas barrier laminate according to [12] or [13] above,
A gas barrier laminate including an aluminum oxide layer in which the inorganic layer is made of aluminum oxide.

According to the present invention, it is possible to provide a gas barrier material with an excellent balance of barrier properties, delamination resistance, and productivity.

1 is a cross-sectional view schematically showing an example of the structure of a gas barrier laminate according to an embodiment of the present invention. 1 is a cross-sectional view schematically showing an example of the structure of a gas barrier laminate according to an embodiment of the present invention.

Embodiments of the present invention will be described below with reference to the drawings. Note that the figure is a schematic diagram and does not correspond to the actual dimensional ratio. In addition, unless otherwise specified, "~" between numbers in the text represents the following from the above.

<Gas barrier film>
The gas barrier film according to the present embodiment is a gas barrier film composed of a cured product of a mixture containing a polycarboxylic acid, a polyamine compound, and a polyvalent metal compound, and the gas barrier film has an infrared absorption spectrum. In, the total peak area in the absorption band 1493 cm ^-1 to 1780 cm ^-1 is A, the total peak area in the absorption band 1598 cm ^-1 to 1690 cm ^-1 is B, and the absorption band 1690 cm ^-1 to 1780 cm ^- When the total peak area in the range of ¹ or less is C, and the total peak area in the absorption band 1493 cm ^-1 or more and 1598 cm ^{-1 or} less is D, the area ratio of the amide bond expressed as B/A is 0.380 or less The area ratio of carboxylic acid represented by C/A is 0.150 or less, and the area ratio of carboxylic acid salt represented by D/A is 0.520 or more.
The gas barrier film according to the present embodiment can be formed by, for example, applying a gas barrier coating material to a base layer or an inorganic layer, followed by drying and heat treatment to harden the gas barrier coating material to form a gas barrier layer. This is obtained by That is, it is obtained by curing a gas barrier coating material.

Further, in the infrared absorption spectrum of the gas barrier film 10 or gas barrier layer 103 according to the present embodiment, the total peak area in the absorption band 1493 cm ^-1 to 1780 cm ^-1 is defined as A, and the absorption band 1598 cm ^-1 to 1690 cm ^- When the total peak area in the range of ¹ or less is defined as B, the area ratio of the amide bond represented by B/A is preferably 0.0000000000000000 from the viewpoint of further improving the balance of barrier properties, delaminated resistance, and productivity. It is 370 or less, more preferably 0.360 or less, even more preferably 0.350 or less. In addition, the lower limit of the area ratio of amide bonds expressed by B/A is set from the viewpoint of further improving gas barrier performance under high humidity, gas barrier performance after retort processing, gas barrier performance when filled with acidic contents, etc. , preferably 0.235 or more, more preferably 0.250 or more, still more preferably 0.270 or more, even more preferably 0.290 or more, particularly preferably 0.310 or more.
Further, in the infrared absorption spectrum of the gas barrier film 10 or the gas barrier layer 103 according to the present embodiment, when the total peak area in the absorption band range of 1690 cm ^-1 to 1780 cm ^-1 is C, it is expressed as C/A. The area ratio of carboxylic acid is preferably 0.120 or less, more preferably 0.120 or less, from the viewpoint of further improving gas barrier performance under high humidity, gas barrier performance after retort treatment, gas barrier performance when filled with acidic contents, etc. is 0.100 or less, more preferably 0.080 or less, particularly preferably 0.060 or less.
Further, the lower limit of the area ratio of carboxylic acid represented by C/A is not particularly limited, but is, for example, 0.0001 or more.
Furthermore, in the infrared absorption spectrum of the gas barrier film 10 or the gas barrier layer 103 according to the present embodiment, when the total peak area in the absorption band range of 1493 cm ^-1 to 1598 cm ^-1 is D, it is expressed as D/A. The area ratio of the carboxylic acid salt is preferably 0.550 or more, more preferably 0.580 or more, and even more preferably 0.600 or more, from the viewpoint of further improving the balance between barrier properties, delamination resistance, and productivity. be.
In addition, the upper limit of the area ratio of the carboxylate salt represented by D/A above further improves gas barrier performance under high humidity, gas barrier performance after retort processing, gas barrier performance when filled with acidic contents, etc. From this point of view, it is preferably 0.750 or less, more preferably 0.720 or less, even more preferably 0.700 or less, and even more preferably 0.680 or less.

In the gas barrier film or gas barrier layer according to the present embodiment, absorption based on νC=O of unreacted carboxylic acid is seen near 1700 cm ⁻¹ in the infrared absorption spectrum, and absorption based on νC=O of the amide bond, which is a crosslinked structure, is observed at around 1700 cm −1. Absorption is observed in the vicinity of 1630 to 1685 cm ^-1 , and absorption based on νC=O of the carboxylate is observed in the vicinity of 1540 to 1560 cm ^-1 .
That is, in this embodiment, the total peak area A in the absorption band 1493 cm ^-1 to 1780 cm ^-1 in the infrared absorption spectrum represents an index of the total amount of carboxylic acid, amide bond, and carboxylate, and the absorption band 1598 cm The total peak area B in the range from ⁻¹ to 1690 cm and ⁻¹ is considered to represent an index of the amount of amide bonds present. Furthermore, the total peak area C in the absorption band range from 1690 cm ^-1 to 1780 cm ^-1 represents an index of the amount of unreacted carboxylic acid, and the total peak area D in the absorption band range from 1493 cm ^-1 to 1598 cm ^-1 is considered to represent an index of the amount of carboxylate present.

In addition, in this embodiment, the above-mentioned total peak areas A to D can be measured by the following procedure.
First, a 1 cm x 3 cm measurement sample is cut out from the gas barrier film or gas barrier layer. Next, an infrared absorption spectrum of the surface of the gas barrier film or gas barrier layer is obtained by infrared total reflection measurement (ATR method). From the obtained infrared absorption spectrum, the total peak areas A to D are calculated using the following steps (1) to (4).
(1) Connect the absorbance at 1780 cm ^-1 and 1493 cm ^-1 with a straight line (N), and define the total peak area A as the area surrounded by N and the absorption spectrum in the range of absorption band 1493 cm ^-1 to 1780 cm ^-1 .
(2) Draw a straight line (O) perpendicularly from the absorbance (Q) at 1690 cm ^-1 , set the intersection of N and O as P, and draw a straight line (S) perpendicularly from the absorbance (R) at 1598 cm ^-1 , and The intersection of S is defined as T, and the area surrounded by the absorption spectrum in the range of absorption band 1598 cm ^-1 to 1690 cm ^-1 , line S, point T, line N, point P, line O, absorbance Q, and absorbance R is the total peak. Let the area be B.
(3) The area surrounded by the absorption spectrum and absorbance Q in the absorption band range of 1690 cm ^-1 to 1780 cm ^-1 , the straight line O, the point P, and the straight line N is the total peak area C.
(4) The area surrounded by the absorption spectrum and absorbance R in the absorption band range of 1493 cm ^-1 to 1598 cm ^-1 , straight line S, point T, and straight line N is defined as the total peak area D.
Next, the area ratios B/A, C/A, and D/A are determined from the areas determined by the above method.
The measurement of the infrared absorption spectrum (infrared total reflection measurement: ATR method) of this embodiment is carried out using, for example, an IRT-5200 device manufactured by JASCO Corporation, with a PKM-GE-S (Germanium) crystal attached and the incident angle This can be carried out under the conditions of 45 degrees Celsius, room temperature, resolution 4 cm ⁻¹ , and 100 integrations.

The area ratio of amide bond represented by B/A, the area ratio of carboxylic acid represented by C/A, and the area ratio of carboxylic acid salt represented by D/A of the gas barrier film or gas barrier layer according to the present embodiment are can be controlled by appropriately adjusting the manufacturing conditions of the gas barrier film or gas barrier layer.
In this embodiment, the blending ratio of the polycarboxylic acid and the polyamine compound, the preparation method of the gas barrier coating material, the method, temperature, time, etc. of the heat treatment of the gas barrier coating material are particularly important for the amide represented by B/A. These factors are listed as factors for controlling the area ratio of bonding, the area ratio of carboxylic acid represented by C/A above, and the area ratio of carboxylic acid salt represented by D/A above.

In this embodiment, (number of moles of polyvalent metal compound in gas barrier coating material)/(number of moles of -COO- group contained in polycarboxylic acid in gas barrier coating material), that is, (number of moles of polyvalent metal compound in cured product) The ratio (number of moles of polyvalent metal derived from the metal compound)/(number of moles of -COO- group derived from polycarboxylic acid in the cured product) is preferably 0.16 or more, more preferably 0.18 or more, and 0.20 The above is more preferable, 0.25 or more is even more preferable, 0.30 or more is even more preferable, and 0.35 or more is even more preferable.
By setting (number of moles of polyvalent metal compound in gas barrier coating material)/(number of moles of -COO- group contained in polycarboxylic acid in gas barrier coating material) to the above lower limit value, it is possible to The gas barrier performance, the gas barrier performance after retort treatment, the gas barrier performance when filled with acidic contents, etc. can be further improved.
According to the studies conducted by the present inventors, when a hygroscopic polyamide or the like is used as the base material layer, gas barrier performance under high humidity, gas barrier performance after retort processing, and filling with acidic contents can be improved. It has been found that gas barrier performance etc. tend to deteriorate when However, by setting (number of moles of polyvalent metal compound in gas barrier coating material)/(number of moles of -COO- group contained in polycarboxylic acid in gas barrier coating material) to the above lower limit value, Even when using hygroscopic polyamide etc. as the material layer, it is possible to improve gas barrier performance under high humidity, gas barrier performance after retort processing, gas barrier performance when filled with acidic contents, etc. .
On the other hand, (number of moles of polyvalent metal compound in gas barrier coating material)/(number of moles of -COO- group contained in polycarboxylic acid in gas barrier coating material), that is, (derived from polyvalent metal compound in cured product) The ratio (number of moles of polyvalent metal)/(number of moles of -COO- group derived from polycarboxylic acid in the cured product) is preferably 0.80 or less, more preferably 0.70 or less, and still more preferably 0.60 or less. It is preferably 0.50 or less, and even more preferably 0.50 or less.
By setting (number of moles of polyvalent metal compound in gas barrier coating material)/(number of moles of -COO- group contained in polycarboxylic acid in gas barrier coating material) below the above upper limit, it is possible to The gas barrier performance, the gas barrier performance after retort treatment, the gas barrier performance when filled with acidic contents, etc. can be further improved.
According to this embodiment, a gas barrier film and a gas barrier laminate having excellent barrier properties and delamination resistance can be obtained even if the heat treatment time is short. That is, according to the present embodiment, it is possible to provide a gas barrier material with an excellent balance of barrier properties, delamination resistance, and productivity.

(Polycarboxylic acid)
A polycarboxylic acid has two or more carboxy groups in its 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-hexenedioic acid, or these Examples include copolymers of It may also be a copolymer of the above α,β-unsaturated carboxylic acid and esters such as ethyl ester, olefins such as ethylene, and the like.
Among these, homopolymers or copolymers of acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, and cinnamic acid are preferred, and polyacrylic acid, polymethacrylic acid, and copolymers of acrylic acid and methacrylic acid are preferred. It is more preferable to use one or more types of polymers selected from polymers, even more preferably at least one type of polymer selected from polyacrylic acid and polymethacrylic acid, and homopolymers of acrylic acid. It is particularly preferably at least one kind of polymer selected from homopolymers of methacrylic acid and methacrylic acid.
Here, in this embodiment, 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 structural units derived from acrylic acid in 100% by mass of the polymer, usually at least 90% by mass, preferably at least 95% by mass, and more. Preferably it contains 99% by mass or more.
Moreover, in this embodiment, polymethacrylic acid includes both a homopolymer of methacrylic acid and a copolymer of methacrylic acid and other monomers. In the case of a copolymer of methacrylic acid and other monomers, polymethacrylic acid contains structural units derived from methacrylic acid in 100% by mass of the polymer, usually at least 90% by mass, preferably at least 95% by mass, and more. Preferably it contains 99% by mass or more.

The polycarboxylic acid according to this embodiment is a polymer obtained by polymerizing carboxylic acid monomers, and the molecular weight of the polycarboxylic acid is preferably 500 to 2,500,000 from the viewpoint of excellent balance between gas barrier properties and handleability. ,000 to 2,000,000 is more preferable, 10,000 to 1,500,000 is more preferable, and even more preferably 100,000 to 1,200,000.
Here, in this embodiment, the molecular weight of the polycarboxylic acid is a weight average molecular weight in terms of polyethylene oxide, and can be measured using gel permeation chromatography (GPC).

By neutralizing the polycarboxylic acid with the volatile base according to the present embodiment, gelation can be suppressed when mixing the polyvalent metal compound or polyamine compound with the polycarboxylic acid. Therefore, in the polycarboxylic acid, it is preferable to use a volatile base to partially or completely neutralize the carboxy group from the viewpoint of preventing gelation. Neutralized products can be obtained by partially or completely neutralizing the carboxy groups of polycarboxylic acids with volatile bases (i.e., partially or completely converting the carboxy groups of polycarboxylic acids into carboxylic acid salts). I can do it. This makes it possible to prevent gelation when adding a polyamine compound or a polyvalent metal compound.
A partially neutralized product is prepared by adding a volatile base to an aqueous solution of a polycarboxylic acid polymer, and the desired degree of neutralization can be achieved by adjusting the quantitative ratio of the polycarboxylic acid and the volatile base. I can do it. In this embodiment, the degree of neutralization of the polycarboxylic acid with the volatile base is preferably 70 to 300 equivalent %, from the viewpoint of sufficiently suppressing gelation caused by the neutralization reaction with the amino group of the polyamine compound, and 90 It is more preferably from 100 to 200 equivalent %, and even more preferably from 100 to 200 equivalent %.

Any water-soluble base can be used as the volatile base.
Examples of the volatile base include tertiary amines such as ammonia, morpholine, alkylamines, 2-dimethylaminoethanol, N-methylmonophorine, ethylenediamine, triethylamine, aqueous solutions thereof, or mixtures thereof. From the viewpoint of obtaining good gas barrier properties, an ammonia aqueous solution is preferred.

(Polyamine compound)
The gas barrier coating material according to this embodiment contains a polyamine compound. By including the polyamine compound, the barrier properties of the gas barrier material obtained can be improved, and the interlayer adhesion of the gas barrier laminate obtained can be improved, and the delamination resistance can be improved.
The polyamine compound according to this embodiment is a polymer having two or more amino groups in its main chain, side chain, or terminal. Specifically, aliphatic polyamines such as polyallylamine, polyvinylamine, polyethyleneimine, and poly(trimethyleneimine); polyamides having amino groups in side chains such as polylysine and polyarginine; and the like. It may also be a polyamine in which some of the amino groups are modified. From the viewpoint of obtaining good gas barrier properties, polyethyleneimine is more preferred.

The number average molecular weight of the polyamine compound according to this embodiment is preferably from 50 to 2,000,000, more preferably from 100 to 1,000,000, and from 1,500 to 500,000 is even more preferred, 1,500 to 100,000 is even more preferred, 1,500 to 50,000 is even more preferred, 3,500 to 20,000 is even more preferred, 5,000 to 15,000 is even more preferred, and 7,000 to 12,000 is particularly preferred.
Here, in this embodiment, the molecular weight of the polyamine compound can be measured using a boiling point elevation method or a viscosity method.

Polyvalent metal compounds are metals and metal compounds belonging to Groups 2 to 13 of the periodic table, and specifically include magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and iron (Fe). ), divalent or higher valent metals such as cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), aluminum (Al), oxides, hydroxides, halides, carbonates of these metals, Examples include phosphates, phosphites, hypophosphites, sulfates, and sulfites. From the viewpoint of water resistance, impurities, etc., metal oxides or metal hydroxides are preferred.
Among the above divalent or higher valent metals, Mg, Ca, Zn, Ba and Al, particularly Zn, are preferred. Among the above metal compounds, divalent or higher valent metal compounds are preferred, and divalent metals such as magnesium oxide, calcium oxide, barium oxide, zinc oxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide, etc. Compounds are more preferred, zinc oxide and zinc hydroxide are even more preferred, and zinc oxide is particularly preferred.
At least one type of these polyvalent metal compounds may be used, and one or more types may be used.

In this embodiment, (number of moles of amino groups contained in the polyamine compound in the gas barrier coating material)/(number of moles of -COO- groups contained in the polycarboxylic acid in the gas barrier coating material), that is, (number of moles of -COO- groups contained in the polycarboxylic acid in the gas barrier coating material) The ratio (number of moles of amino groups derived from the polyamine compound)/(number of moles of -COO- groups derived from polycarboxylic acid in the cured product) is preferably 20/100 or more, more preferably 25/100 or more, and 30/100. The ratio is more preferably 35/100 or more, even more preferably 40/100 or more. By setting (number of moles of amino groups contained in the polyamine compound in the coating material for gas barrier)/(number of moles of -COO- group contained in the polycarboxylic acid in the coating material for gas barrier) to the above lower limit value or more, Gas barrier performance under high humidity, gas barrier performance after retort treatment, gas barrier performance when filled with acidic contents, etc. can be further improved.
On the other hand, (number of moles of amino groups contained in the polyamine compound in the gas barrier coating material)/(number of moles of -COO- groups contained in the polycarboxylic acid in the gas barrier coating material), that is, (number of moles of the -COO- group contained in the polycarboxylic acid in the gas barrier coating material) The ratio (number of moles of amino groups derived from polycarboxylic acid)/(number of moles of -COO- groups derived from polycarboxylic acid in the cured product) is preferably 90/100 or less, more preferably 85/100 or less, and furthermore 80/100 or less. It is preferably 75/100 or less, even more preferably 70/100 or less. By setting (number of moles of amino groups contained in the polyamine compound in the coating material for gas barrier)/(number of moles of -COO- group contained in the polycarboxylic acid in the coating material for gas barrier) below the above upper limit, Gas barrier performance under high humidity, gas barrier performance after retort treatment, gas barrier performance when filled with acidic contents, etc. can be further improved.
The details of this reason are not clear, but the amide crosslinks due to the amino groups constituting the polyamine compound and the metal crosslinks due to the polyvalent metals constituting the salt of polycarboxylic acid and polyvalent metal form a well-balanced and dense structure. It is thought that by doing so, it is possible to obtain a gas barrier film or gas barrier laminate that has excellent gas barrier performance under high humidity, gas barrier performance after retort treatment, and gas barrier performance when filled with acidic contents.

It is preferable that the gas barrier coating material according to this embodiment further contains a carbonate ammonium salt. A carbonate ammonium salt is added to convert a polyvalent metal compound into a polyvalent metal ammonium carbonate complex, improve the solubility of the polyvalent metal compound, and prepare a uniform solution containing the polyvalent metal compound. It is something. By containing the carbonate ammonium salt, the gas barrier coating material according to the present embodiment can increase the amount of dissolved polyvalent metal compound, and as a result, (the number of moles of the polyvalent metal compound in the gas barrier coating material) Even if /(number of moles of -COO- groups contained in polycarboxylic acid in the gas barrier coating material) is greater than or equal to the above lower limit, a uniform gas barrier coating material can be obtained.
Examples of carbonate-based ammonium salts include ammonium carbonate and ammonium hydrogen carbonate.Ammonium carbonate is preferred because it easily evaporates and is difficult to remain in the resulting gas barrier layer.
(Number of moles of ammonium carbonate salt in gas barrier coating material)/(Number of moles of polyvalent metal compound in gas barrier coating material) is preferably 0.05 or more, more preferably 0.10 or more, and 0.05 or more, more preferably 0.10 or more. It is more preferably 25 or more, even more preferably 0.50 or more, and particularly preferably 0.75 or more. Thereby, the solubility of the polyvalent metal compound can be further improved.
On the other hand, (number of moles of carbonate ammonium salt in gas barrier coating material)/(number of moles of polyvalent metal compound in gas barrier coating material) is preferably 10.0 or less, more preferably 5.0 or less, It is more preferably 2.0 or less, and even more preferably 1.5 or less. Thereby, the coating properties of the gas barrier coating material according to this embodiment can be further improved.

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 coatability.

Further, it is preferable to further add a surfactant to the gas barrier coating material from the viewpoint of suppressing the occurrence of repelling 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.

Examples of the surfactant according to the present embodiment include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, etc., from the viewpoint of obtaining good coating properties. From these, nonionic surfactants are preferred, and polyoxyethylene alkyl ethers are more preferred.

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

Examples of the polyoxyalkylene alkylaryl ethers include polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, and the like.
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 esters include polyoxyethylene oleate, polyoxyethylene laurate, and polyoxyethylene distearate.
Examples of the sorbitan fatty acid esters include sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquiolate, polyoxyethylene monooleate, and polyoxyethylene stearate.
Examples of silicone surfactants include dimethylpolysiloxane.
Examples of acetylene alcohol surfactants include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3, Examples include 5-dimethyl-1-hexyn-3ol.
Examples of the fluorine-containing surfactant include fluorine alkyl esters.

The gas barrier coating material according to the present embodiment 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, antifogging agents, pigments, dyes, inorganic or organic fillers, etc. may be added.

<Method for manufacturing gas barrier coating material>
The gas barrier coating material according to this embodiment can be manufactured, for example, as follows.
First, a volatile base is added to the polycarboxylic acid to completely or partially neutralize the carboxy groups of the polycarboxylic acid. Further, by mixing a polyvalent metal salt compound and a carbonate ammonium salt, all or a part of the carboxy groups of the polycarboxylic acid are neutralized with the volatile base, and the carboxy groups of the polycarboxylic acid that are not neutralized with the volatile base are mixed. A metal salt is formed at the carboxy group of the polycarboxylic acid. Thereafter, a gas barrier coating material is obtained by further adding a polyamine compound. By mixing a polycarboxylic acid, a polyvalent metal salt compound, a carbonate ammonium salt, and a polyamine compound in such a procedure, the formation of aggregates can be suppressed and a uniform gas barrier coating material can be obtained. This allows the dehydration condensation reaction between the -COO- group contained in the polycarboxylic acid and the amino group contained in the polyamine compound to proceed more effectively.

More details are as follows.
First, a completely or partially neutralized solution of the carboxy groups constituting the polycarboxylic acid is prepared.
A volatile base is added to the polycarboxylic acid to completely or partially neutralize the carboxy groups of the polycarboxylic acid. By neutralizing the carboxy groups of the polycarboxylic acid, the carboxy groups that make up the polycarboxylic acid react with the amino groups that make up the polyvalent metal compound or polyamine compound when the polyvalent metal compound or polyamine compound is added. It is possible to effectively prevent gelation caused by this, and obtain a uniform gas barrier coating material.
Next, a polyvalent metal salt compound and a carbonate ammonium salt are added and dissolved, and the generated polyvalent metal ions form a polyvalent metal salt with the -COO- group constituting the polycarboxylic acid. In this case, the -COO- group that forms a salt with a polyvalent metal ion refers to both the carboxy group that was not neutralized with the base and the -COO- group that was neutralized by the base. In the case of a -COO- group neutralized with a base, the polyvalent metal ions derived from the polyvalent metal compound exchange and coordinate to form a polyvalent metal salt of the -COO- group. A gas barrier coating material can be obtained by further adding a polyamine compound after forming the polyvalent metal salt.

The gas barrier coating material produced in this manner is applied onto the base layer, dried and cured to form a gas barrier layer. At this time, the polyvalent metal of the polyvalent metal salt of the -COO- group constituting the polycarboxylic acid forms a metal crosslink, and the amino group constituting the polyamine forms an amide crosslink, resulting in a gas barrier with excellent gas barrier properties. A sexual layer is obtained.

<Gas barrier laminate>
1 and 2 are cross-sectional views schematically showing an example of the structure of a gas barrier laminate 100 according to an embodiment of the present invention.
The gas barrier laminate 100 according to this embodiment has a gas barrier layer 103 formed by applying and curing a gas barrier coating material on a base layer 101 .
That is, the gas barrier laminate 100 according to the present embodiment includes a base layer 101 and a gas barrier film 10 provided on at least one surface of the base layer 101 and composed of the gas barrier film 10 according to the present embodiment. A layer 103.
Further, as shown in FIG. 2, in the gas barrier laminate 100, an inorganic layer 102 may be further laminated between the base layer 101 and the gas barrier layer 103 (gas barrier film 10). Thereby, barrier performance such as oxygen barrier property and water vapor barrier property can be further improved.
Furthermore, in the gas barrier laminate 100, an undercoat layer may be further laminated on the base layer 101 from the viewpoint of improving the adhesion between the base layer 101 and the gas barrier layer 103 or the inorganic layer 102. .

(Inorganic layer)
Examples of the inorganic substance constituting the inorganic layer 102 according to this embodiment include metals, metal oxides, metal nitrides, metal fluorides, metal oxynitrides, and the like that can form a thin film having barrier properties.
Examples of the inorganic material forming the inorganic material layer 102 include elements of group 2A of the periodic table such as beryllium, magnesium, calcium, strontium, and barium; transition elements of the periodic table such as titanium, zirconium, ruthenium, hafnium, and tantalum; and periodic table elements such as zinc. Group 2B elements; Group 3A elements of the periodic table such as aluminum, gallium, indium, and thallium; Elements of group 4A of the periodic table such as silicon, germanium, and tin; Elements, oxides, and nitrides of group 6A elements of the periodic table such as selenium and tellurium Examples include one or more selected from compounds, fluorides, oxynitrides, and the like.
Note that in this embodiment, group names in the periodic table are shown in the old CAS format.

Furthermore, among the above-mentioned inorganic substances, one or more inorganic substances selected from the group consisting of silicon oxide, aluminum oxide, and aluminum are preferred, and aluminum oxide is more preferable, since it has an excellent balance of barrier properties, cost, etc. .
Note that silicon oxide may contain silicon monoxide and silicon suboxide in addition to silicon dioxide.

The inorganic material layer 102 is formed of the above-mentioned inorganic material. The inorganic layer 102 may be composed of a single inorganic layer, or may be composed of a plurality of inorganic layers. Furthermore, 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 different types of inorganic layers.

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, from the viewpoint of a balance of barrier properties, adhesion, and handleability.
In this embodiment, the thickness of the inorganic layer 102 can be determined from an image observed using a transmission electron microscope or a scanning electron microscope.

The method for forming the inorganic layer 102 is not particularly limited, and includes, for example, a vacuum 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 or both sides of the base layer 101 by a method, a sol-gel method, or the like. Among these, film formation under reduced pressure such as sputtering, ion plating, chemical vapor deposition (CVD), physical vapor deposition (PVD), and plasma CVD is preferable. As a result, chemically active molecular species containing silicon such as silicon nitride and silicon oxynitride react quickly, 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 atoms or compounds are chemically active molecular or atomic species.

(Base material layer)
The base material layer 101 according to the present embodiment is not particularly limited and can be used as long as it can be coated with a solution of a gas barrier coating material. For example, thermosetting resins, thermoplastic resins, organic materials such as paper, glass, ceramics, silicon oxide, silicon oxynitride, silicon nitride, cement, aluminum, aluminum oxide, metals such as iron, copper, stainless steel, etc. Examples include inorganic materials, multilayer base material layers made of a combination of organic materials, or a combination of an organic material and an inorganic material. Among these, for example, in the case of various film applications such as packaging materials and panels, plastic films using thermosetting resins or thermoplastic resins, or organic materials such as paper are preferable.

As the thermosetting resin, a known thermosetting resin can be used. Examples include epoxy resin, unsaturated polyester resin, phenol resin, urea/melamine resin, polyurethane resin, silicone resin, polyimide, and the like.

As the thermoplastic resin, a known thermoplastic resin can be used. For example, polyolefins (polyethylene, polypropylene, poly(4-methyl-1-pentene), poly(1-butene), etc.), polyesters (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), polyamides (nylon-6, nylon -66, polymethaxylene adipamide, etc.), polyvinyl chloride, polyimide, ethylene/vinyl acetate copolymer or its saponified product, polyvinyl alcohol, polyacrylonitrile, polycarbonate, polystyrene, ionomer, fluororesin, or mixtures thereof, etc. Can be mentioned.
Among these, from the viewpoint of improving transparency, one or more resins selected from the group consisting of polypropylene, polyethylene terephthalate, polyethylene naphthalate, polyamide, polyimide, and polybutylene terephthalate are preferred, and pinhole resistance is preferred. From the viewpoint of excellent tear resistance, heat resistance, etc., one or more resins selected from the group consisting of polyamide, polyethylene terephthalate, and polybutylene terephthalate are preferred. In addition, when hygroscopic polyamide is used as the base material layer, the polyamide absorbs moisture and swells in the gas barrier laminate, resulting in poor gas barrier performance under high humidity, gas barrier performance after retort processing, and acidic content. Gas barrier performance etc. tend to deteriorate when filled with materials, but the gas barrier laminate 100 according to this embodiment has good gas barrier performance under high humidity even when hygroscopic polyamide is used as the base layer 101. Deterioration in gas barrier performance after retort treatment can be suppressed.
Moreover, the base material layer 101 made of thermoplastic resin may be a single layer or may be a layer of two or more types depending on the use of the gas barrier laminate 100.
Further, a film formed from the above thermosetting resin or thermoplastic resin may be stretched in at least one direction, preferably in two axial directions, to form the base material layer.

The base material layer 101 according to this embodiment is made of one or more selected from polypropylene, polyethylene terephthalate, polyethylene naphthalate, polyamide, polyimide, and polybutylene terephthalate from the viewpoint of excellent transparency, rigidity, and heat resistance. A biaxially stretched film formed of a thermoplastic resin is preferred, and a biaxially stretched film formed of one or more thermoplastic resins selected from polyamide, polyethylene terephthalate, and polybutylene terephthalate is more preferred.

In the gas barrier laminate 100 according to the present embodiment, the base layer 101 includes a first base layer and a second base layer, and the gas barrier layer 103, the first base layer, and the second base layer are arranged in this order. In the case of a laminated structure, the first base layer preferably contains one or more resins selected from the group consisting of polyamide, polyethylene terephthalate, and polybutylene terephthalate, and more preferably contains polyamide. . In this case, the base layer 101 preferably contains polyolefin (polyethylene, polypropylene, poly(4-methyl-1-pentene), poly(1-butene), etc.) that has excellent water resistance.
As a result, in the gas barrier laminate 100 according to the present embodiment, while improving pinhole resistance, tear resistance, heat resistance, etc., deterioration of gas barrier performance under high humidity and gas barrier performance after retort processing is further suppressed. Can be suppressed.

Further, the surface of the base layer 101 may be coated with polyvinylidene chloride, polyvinyl alcohol, ethylene/vinyl alcohol copolymer, acrylic resin, urethane resin, or the like.
Furthermore, the base layer 101 may be subjected to surface treatment in order to improve adhesiveness with the gas barrier layer 103 (gas barrier film 10). 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 properties.

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

(undercoat layer)
In the gas barrier laminate 100, from the viewpoint of improving the adhesion between the base layer 101 and the gas barrier layer 103 or the inorganic layer 102, an undercoat layer, preferably an epoxy (meth)acrylate type, is provided on the surface of the base layer 101. It is preferable to form an undercoat layer of a compound or a urethane (meth)acrylate compound.
The undercoat layer is preferably a layer formed by curing at least one selected from epoxy (meth)acrylate compounds and urethane (meth)acrylate compounds.

Epoxy (meth)acrylate compounds include epoxy compounds such as bisphenol A epoxy compounds, bisphenol F epoxy compounds, bisphenol S epoxy compounds, phenol novolak epoxy compounds, cresol novolak epoxy compounds, aliphatic epoxy compounds, and acrylics. Examples include compounds obtained by reacting acids or methacrylic acid, and acid-modified epoxy (meth)acrylates obtained by reacting the above epoxy compounds with carboxylic acids or their anhydrides. These epoxy (meth)acrylate compounds are applied to the surface of the base layer together with a photopolymerization initiator and, if necessary, a diluent consisting of another photopolymerization initiator or a heat-reactive monomer, and then exposed to ultraviolet light, etc. An undercoat layer is formed by crosslinking reaction.

Examples of the urethane (meth)acrylate compounds include those obtained by acrylating an oligomer (hereinafter also referred to as a polyurethane oligomer) consisting of a polyol compound and a polyisocyanate compound.
A polyurethane oligomer can be obtained from a condensation product of a polyisocyanate compound and a polyol compound. Specific polyisocyanate compounds include methylene bis(p-phenylene diisocyanate), hexamethylene diisocyanate/hexanetriol adduct, hexamethylene diisocyanate, tolylene diisocyanate, tolylene diisocyanate trimethylolpropane adduct, 1,5 Examples include -naphthylene diisocyanate, thiopropyl diisocyanate, ethylbenzene-2,4-diisocyanate, 2,4-tolylene diisocyanate dimer, hydrogenated xylylene diisocyanate, tris(4-phenylisocyanate) thiophosphate, etc. Specific polyol compounds include polyether polyols such as polyoxytetramethylene glycol, polyester polyols such as polyadipate polyols and polycarbonate polyols, and copolymers of acrylic esters and hydroxyethyl methacrylate. Monomers constituting acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, Examples include phenyl (meth)acrylate.
These epoxy (meth)acrylate compounds and urethane (meth)acrylate compounds are used in combination, if necessary. In addition, methods for polymerizing these include various known methods, specifically methods by irradiation with energy rays including ionizing radiation, heating, and the like.

When the undercoat layer is formed by curing with ultraviolet rays, acetophenones, benzophenones, mifilabenzoyl benzoate, α-amyloxime ester, or thioxanthone are used as photopolymerization initiators, and n-butylamine, triethylamine, triethylamine, etc. It is preferable to use n-butylphosphine or the like in combination as a photosensitizer. Further, in this embodiment, the epoxy (meth)acrylate compound and the urethane (meth)acrylate compound are also used in combination.

Further, these epoxy (meth)acrylate compounds and urethane (meth)acrylate compounds are diluted with a (meth)acrylic monomer. Examples of such (meth)acrylic monomers include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, methoxyethyl (meth)acrylate, and butoxyethyl (meth)acrylate. Acrylate, phenyl(meth)acrylate, trimethylolpropane tri(meth)acrylate, hexanediol(meth)acrylate, tripropylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate as a polyfunctional monomer Examples include acrylate, dipentaerythritol hexa(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate.
Among these, when a urethane (meth)acrylate compound is used as the undercoat layer, the oxygen gas barrier properties of the resulting gas barrier laminate 100 are further improved.
The thickness of the undercoat layer of this embodiment is generally in the range of 0.01 to 100 g/m ² , preferably 0.05 to 50 g/m ² in terms of coating amount.

(Adhesive layer)
Further, an adhesive layer may be provided between the base layer 101 and the gas barrier layer 103 (gas barrier film 10). Note that the undercoat layer is excluded from the adhesive layer.
The adhesive layer may contain any known adhesive. The adhesive is composed of organic titanium resin, polyethylene imine resin, urethane resin, epoxy resin, acrylic resin, polyester resin, oxazoline group-containing resin, modified silicone resin, alkyl titanate, polyester polybutadiene, etc. Examples include laminating adhesives, one-component and two-component polyols and polyvalent isocyanates, water-based urethanes, and ionomers. Alternatively, a water-based adhesive mainly made of acrylic resin, vinyl acetate resin, urethane resin, polyester resin, etc. may be used.
Further, depending on the use of the gas barrier laminate 100, other additives such as a curing agent and a silane coupling agent may be added to the adhesive. If the gas barrier laminate is to be used in hot water treatment such as retorts, from the viewpoint of heat resistance and water resistance, dry laminating adhesives such as polyurethane adhesives are preferred, and solvent-based adhesives are preferred. A two-component curing type polyurethane adhesive is more preferred.

The gas barrier laminate 100 and the gas barrier film 10 according to the present embodiment have excellent gas barrier performance, and can be used in packaging materials, especially food packaging materials for contents that require high gas barrier properties, medical applications, industrial applications, etc. It can also be suitably used as a variety of packaging materials such as for everyday miscellaneous goods.
Further, the gas barrier laminate 100 and the gas barrier film 10 of the present embodiment are, for example, a vacuum insulation film that requires high barrier performance; a sealing film for sealing an electroluminescent element, a solar cell, etc. It can be suitably used as a film, etc.

<Method for manufacturing gas barrier laminate>
The method for manufacturing the gas barrier laminate 100 according to the present embodiment includes the steps of applying the gas barrier coating material according to the present embodiment to the base layer 101 and then drying to obtain a coated layer, and The method includes a step of heating the carbon 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 to form a gas barrier layer 103 having an amide bond.

The method for applying the gas barrier coating material according to the present embodiment to the base layer 101 is not particularly limited, and a normal method can be used. For example, Meyer bar coater, air knife coater, direct gravure coater, gravure offset, arc gravure coater, gravure reverse and jet nozzle type gravure coaters, reverse rolls such as top feed reverse coater, bottom feed reverse coater and nozzle feed reverse coater. Examples include coating methods using various known coating machines such as a coater, a five-roll coater, a lip coater, a bar coater, a bar reverse coater, and a die coater.

The coating amount (wet thickness) is preferably 0.05 to 300 μm, more preferably 1 to 200 μm, and even more preferably 1 to 100 μm.
When the coating amount is less than or equal to the above upper limit, curling of the resulting gas barrier laminate or gas barrier film can be suppressed. Furthermore, when the coating amount is below the above upper limit, it becomes 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.
Moreover, when the coating amount is at least the above lower limit, the barrier performance of the resulting gas barrier laminate or gas barrier film can be made better.
The thickness of the layer containing the gas barrier polymer after drying and curing (the gas barrier layer in the gas barrier laminate or the gas barrier film) is preferably 0.01 μm or more and 15 μm or less, more preferably 0.05 μm or more and 5 μm or less, More preferably, the thickness is 0.1 μm or more and 1 μm or less.

The drying and heat treatment may be performed after drying, or may be performed simultaneously.
The method of drying and heat treatment is not particularly limited as long as it can achieve the purpose of the present invention, but any method that can cure the gas barrier coating material or heat the cured gas barrier coating material may be used. For example, convection heat transfer from ovens and dryers, conductive heat transfer from heating rolls, radiation heat transfer using electromagnetic waves such as infrared, far-infrared, and near-infrared heaters, and internal heat generation from microwaves. can be mentioned. As the device used for drying and heat treatment, it is preferable to use a device that can perform both drying and heat treatment from the viewpoint of manufacturing efficiency. Among these, specifically, it is preferable to use a hot air oven because it can be used for various purposes such as drying, heating, and annealing, and it is preferable to use a heated roll because it has excellent heat conduction efficiency to the film. is preferred. Moreover, the methods used for drying and heat treatment may be combined as appropriate. A hot air oven and a heated roll may be used in combination. For example, if the gas barrier coating material is dried in a hot air oven and then heat treated with a heated roll, the heat treatment step will be shortened, which is preferable from the viewpoint of manufacturing efficiency. Further, it is preferable to perform drying and heat treatment using only a hot air oven.
For example, the heat treatment temperature is 160 to 250°C, the heat treatment time is 1 second to 1 minute, preferably the heat treatment temperature is 180 to 240°C, the heat treatment time is 1 second to 30 seconds, and more preferably the heat treatment temperature is 200°C. It is desirable to carry out the heat treatment at a temperature of 230°C to 230°C for a heat treatment time of 1 second to 15 seconds, more preferably a heat treatment temperature of 200°C to 220°C and a heat treatment time of 1 second to 10 seconds. Further, as described above, by using a heating roll in combination, heat treatment can be performed in a short time. In addition, from the viewpoint of effectively promoting 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 heat treatment time are determined according to the wet thickness of the gas barrier coating material. It is important to make adjustments accordingly.

When gas barrier coating materials are dried and heat treated, the carboxyl groups of polycarboxylic acids react with polyamines and polyvalent metal compounds, resulting in covalent bonds and ionic crosslinking, resulting in good gas barrier properties even under high humidity conditions. is obtained.

Although the embodiments of the present invention have been described above with reference to the drawings, these are merely examples of the present invention, and various configurations other than those described above may also be adopted.

Hereinafter, this embodiment will be described in detail with reference to Examples and Comparative Examples. Note that this embodiment is in no way limited to the description of these examples.

[Example 1]
(1) Preparation of gas barrier coating material 10% ammonia water (Wako Pure Chemical Industries, Ltd.) based on the carboxyl group of polyacrylic acid (manufactured by Toagosei Co., Ltd., product name: AC-10H, weight average molecular weight: 800,000) Ammonia (manufactured by Mimaki Co., Ltd.) was added to the solution at a concentration of 150% by weight, and purified water was further added to obtain an aqueous ammonium polyacrylate solution having a concentration of 7.29% by weight.
Next, zinc oxide (manufactured by Kanto Kagaku Co., Ltd.) and ammonium carbonate were added to the obtained ammonium polyacrylate aqueous solution and mixed and stirred to prepare a mixed solution (A). Here, the amount of zinc oxide added is expressed as (number of moles of zinc oxide in gas barrier coating material)/(number of moles of -COO- group contained in polyacrylic acid in gas barrier coating material) as shown in Table 1. The amount was determined to be the value. Further, ammonium carbonate was used in an amount such that (number of moles of carbonate ammonium salt in the gas barrier coating material)/(number of moles of zinc oxide in the gas barrier coating material) was 1.0.
Next, purified water was added to polyethyleneimine (manufactured by Nippon Shokubai Co., Ltd., product name: SP-200, number average molecular weight: 10,000) to obtain a 10% polyethyleneimine aqueous solution.
Next, the mixed solution (A) and the polyethyleneimine aqueous solution are mixed into (number of moles of amino groups contained in the polyethyleneimine in the gas barrier coating material)/(-) contained in the polyacrylic acid in the gas barrier coating material. A mixed solution (B) was prepared by mixing in such a proportion that the number of moles of COO- group became the value shown in Table 1.
Furthermore, purified water was added so that the solid content concentration of the above mixed solution (B) was 1.5%, and after stirring until a homogeneous solution was obtained, an activator (product name: Emulgen 120 manufactured by Kao Corporation) was mixed. A gas barrier coating material was prepared by mixing the liquid (B) in an amount of 0.3% by weight based on the solid content.

(2) Preparation of gas barrier laminated film The obtained gas barrier coating material was applied to the corona-treated surface of a 12 μm thick biaxially stretched polyethylene terephthalate film (manufactured by Unitika, PET12) with a coating amount after drying with a Meyer bar. It was coated to a thickness of 0.3 μm, dried using a hot air dryer at a temperature of 120°C for 12 seconds, and then heat-treated with a heating roll at a temperature of 210°C for a time of 4.2 seconds. A gas barrier laminate film was obtained.
The obtained gas barrier laminate film was evaluated as follows, and the results are shown in Table 1.

[Examples 2 to 10]
(Number of moles of zinc oxide in gas barrier coating material)/(Number of moles of -COO- group contained in polyacrylic acid in gas barrier coating material) and (Amino group contained in polyethyleneimine in gas barrier coating material) A gas barrier laminate film was prepared in the same manner as in Example 1, except that the ratio (number of moles of -COO- group contained in polyacrylic acid in the gas barrier coating material) was changed to the values shown in Table 1. I got each.
The following evaluations were performed on the obtained gas barrier film, and the results are shown in Table 1.

[Comparative Examples 1, 4 to 6]
(Number of moles of amino groups contained in polyethyleneimine in coating material for gas barrier)/(Number of moles of -COO- group contained in polyacrylic acid in coating material for gas barrier) was changed to the values shown in Table 1, respectively, Further, gas barrier laminate films were obtained in the same manner as in Example 1 except that zinc oxide and ammonium carbonate were not used.
The following evaluations were performed on the obtained gas barrier film, and the results are shown in Table 1.

[Comparative Examples 2-3]
(Number of moles of zinc oxide in gas barrier coating material)/(Number of moles of -COO- group contained in polyacrylic acid in gas barrier coating material) and (Amino group contained in polyethyleneimine in gas barrier coating material) Example 1 was carried out in the same manner as in Example 1 except that (number of moles of )/(number of moles of -COO- group contained in polyacrylic acid in the gas barrier coating material) was changed to the values shown in Table 1, and further, ammonium carbonate was not used. Gas barrier laminate films were obtained respectively.
The following evaluations were performed on the obtained gas barrier film, and the results are shown in Table 1.

[Comparative Examples 7 to 9]
(Number of moles of zinc oxide in gas barrier coating material)/(Number of moles of -COO- group contained in polyacrylic acid in gas barrier coating material) was changed to the values shown in Table 1, and polyethyleneimine was used. Gas barrier laminate films were obtained in the same manner as in Example 1, except that the gas barrier laminate films were not used.
The following evaluations were performed on the obtained gas barrier laminate film, and the results are shown in Table 1.

<Evaluation method>
(1) On both sides of a 15 μm thick polyamide film (manufactured by Unitika, trade name: ONBC), 9 parts by mass of an ester adhesive (polyurethane adhesive (manufactured by Mitsui Chemicals, trade name: Takelac A525S), isocyanate) A system curing agent (manufactured by Mitsui Chemicals, trade name: Takenate A50): 1 part by mass and ethyl acetate: 7.5 parts by mass) were applied. Next, the barrier side (the side coated with the gas barrier coating material) of the gas barrier laminate film obtained in the Examples and Comparative Examples and the unstretched polypropylene film with a thickness of 60 μm ( (manufactured by Mitsui Chemicals Tohcello Co., Ltd., trade name: RXC-22)) to obtain a film before retort processing.

(2) Retort processing (water filling)
The film obtained above before retort treatment is folded back so that the unstretched polypropylene film is on the inside, and two sides are heat-sealed to form a bag. 70cc of water is added as the content, and the other side is heat-sealed. A bag was prepared, and the bag was subjected to retort treatment at 130° C. for 30 minutes using a high-temperature, high-pressure retort sterilizer. After the retort treatment, water was removed from the contents to obtain a film after the retort treatment (water filled).
Note that delamination occurred in the films of Comparative Examples 7 and 8 due to the retort treatment.

(3) Retort processing (grain vinegar filling)
The film obtained above before retort treatment was folded back so that the unstretched polypropylene film was on the inside, and the two sides were heat-sealed to form a bag, and the contents were 70 cc of grain vinegar (pH: 2.4). A bag was prepared by heat-sealing the other side, and the bag was subjected to retort treatment at 130° C. for 30 minutes in a high-temperature, high-pressure retort sterilizer. After the retort treatment, the grain vinegar from the contents was removed to obtain a film after the retort treatment (grain vinegar filling).

(4) Oxygen permeability [ml/( ^m2・day・MPa)]
The oxygen permeability of the film before retort treatment, the film after retort treatment (filled with water), and the film after retort treatment (filled with grain vinegar) obtained by the above method was measured using OX-TRAN 2/21 manufactured by Mocon Co., Ltd. Measurements were made in accordance with JIS K 7126 at a temperature of 20° C. and a humidity of 90% RH.

(5) Water vapor permeability [g/( ^m2・day)]
The film before retort treatment, the film after retort treatment (filled with water), and the film after retort treatment (filled with grain vinegar) obtained by the above method are stacked so that the unstretched polypropylene film faces the inner surface to form a gas barrier laminate film. After folding and heat-sealing three sides to form a bag, put calcium chloride as the contents and heat-seal the other side to make a bag with a surface area of 0.01 ^m2 . %RH for 300 hours, and the water vapor permeability was measured based on the weight difference.

(6) IR area ratio Measurement of infrared absorption spectra (infrared total reflection measurement: ATR method) uses an IRT-5200 device manufactured by JASCO Corporation, with a PKM-GE-S (Germanium) crystal attached and an incident angle of 45 degrees. Measurement was carried out under the conditions of room temperature, resolution of 4 cm ⁻¹ , and 100 integrations. 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 determined from the total peak areas A to D.

(7) Tape Peeling Test The following tape peeling test was conducted on the obtained gas barrier laminate film, and evaluation was made based on the following criteria.
Cellophane tape (Nichiban Cellotape (registered trademark)) was attached to the surface of the gas barrier layer of the produced gas barrier laminate film, and the cellophane tape was peeled off to evaluate how the gas barrier layer peeled off.
〇: No peeling of gas barrier layer ×: Peeling of gas barrier layer

(8) Appearance evaluation of gas barrier laminate film The appearance of the gas barrier laminate film was visually evaluated using the following criteria.
〇: No coloring or spots observed on the surface ×: Coloring or spots observed on the surface

10 Gas barrier film 100 Gas barrier laminate 101 Base layer 102 Inorganic layer 103 Gas barrier layer

Claims (14)

A gas barrier film composed of a cured product of a mixture containing a polycarboxylic acid, a polyamine compound, and a polyvalent metal compound,
In the infrared absorption spectrum of the gas barrier film,
The total peak area in the absorption band range of 1493 cm ^-1 to 1780 cm ^-1 is A,
The total peak area in the absorption band 1598 cm ^-1 to 1690 cm ^-1 is defined as B,
The total peak area in the absorption band 1690 cm ^-1 to 1780 cm ^-1 is C,
When the total peak area in the absorption band 1493 cm ^-1 to 1598 cm ^-1 is D,
The area ratio of the amide bond represented by B/A is 0.250 or more and 0.370 or less (excluding 0.370) ,
The area ratio of carboxylic acid represented by C/A is 0.150 or less,
A gas barrier film having an area ratio of a carboxylic acid salt represented by D/A of 0.520 or more. The gas barrier film according to claim 1,
Gas barrier property where (number of moles of polyvalent metal derived from the polyvalent metal compound in the cured product)/(number of moles of -COO- group derived from the polycarboxylic acid in the cured product) is 0.16 or more film. The gas barrier film according to claim 1 or 2,
A gas barrier in which (number of moles of amino groups derived from the polyamine compound in the cured product)/(number of moles of -COO- groups derived from the polycarboxylic acid in the cured product) is 20/100 or more and 90/100 or less. sex film. The gas barrier film according to any one of claims 1 to 3,
A gas barrier film in which 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. The gas barrier film according to any one of claims 1 to 4,
A gas barrier film in which the polyvalent metal compound contains a metal compound having a valence of two or more. The gas barrier film according to any one of claims 1 to 5,
The polyvalent metal compound contains one or more divalent metal compounds selected from magnesium oxide, calcium oxide, barium oxide, zinc oxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, and zinc hydroxide. Gas barrier film. The gas barrier film according to any one of claims 1 to 6,
A gas barrier film in which the polyamine compound includes polyethyleneimine. a base material layer;
A gas barrier layer provided on at least one surface of the base layer and constituted by the gas barrier film according to any one of claims 1 to 7;
A gas barrier laminate comprising: The gas barrier laminate according to claim 8,
A gas barrier laminate in which the base layer contains one or more resins selected from the group consisting of polyamide, polyethylene terephthalate, and polybutylene terephthalate. The gas barrier laminate according to claim 8 or 9,
The base layer includes a first base layer and a second base layer,
The gas barrier layer, the first base layer, and the second base layer are laminated in this order, and the first base layer is made of a type selected from the group consisting of polyamide, polyethylene terephthalate, and polybutylene terephthalate. Or a gas barrier laminate containing two or more types of resin. The gas barrier laminate according to any one of claims 8 to 10,
A gas barrier laminate, wherein the gas barrier layer has a thickness of 0.01 μm or more and 15 μm or less. The gas barrier laminate according to any one of claims 8 to 11,
A gas barrier laminate further comprising an inorganic layer between the base layer and the gas barrier layer. The gas barrier laminate according to claim 12,
A gas barrier laminate, wherein 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 claim 12 or 13,
A gas barrier laminate including an aluminum oxide layer in which the inorganic layer is made of aluminum oxide.

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