TW201700566A - Method for producing gas-barrier laminate - Google Patents

Abstract

This method for manufacturing a gas-barrier layered product (100) is a method for manufacturing a gas-barrier layered product (100) equipped with a base material layer (101) and a gas-barrier polymer layer (103) provided to at least one surface of the base material layer (101). The method for manufacturing a gas-barrier layered product (100) includes a step for applying a mixture including a polycarboxylic acid and polyamine compound to the base material layer (101) and obtaining a coating layer, and a step for forming a gas-barrier polymer layer (103) having amide bonds by heating the coating layer by a heating means and dehydrocondensing the carboxyl groups included in the polycarboxylic acid and the amino groups included in the polyamine compound. The heating means includes at least one selected from a conductive heat transfer type and a radiant heat transfer type.

Description

Method for producing gas barrier laminated body

The present invention relates to a method of producing a gas barrier layered product.

In general, a gas barrier material is a laminate in which an inorganic layer as a gas barrier layer is provided on a substrate layer. However, the inorganic layer is not resistant to friction or the like, and such a gas barrier layered body may be cracked in the inorganic layer due to friction or elongation during printing at the time of post-processing, lamination, or filling of the contents, resulting in gas barrier properties. Reduced phenomenon. Therefore, the gas barrier material also uses a laminate which uses an organic layer as a gas barrier layer.

As the gas barrier material using the 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. For example, the one described in the patent document 1 (Japanese Patent Laid-Open Publication No. 2005-225940) and the patent document 2 (Japanese Patent Laid-Open Publication No. 2013-10857) .

Patent Document 1 discloses a gas barrier film comprising a gas barrier layer formed of a polycarboxylic acid, a polyamine, and/or a polyhydric alcohol, and the degree of crosslinking of the polycarboxylic acid is 40% or more. Patent Document 1 discloses that such a gas barrier film also has excellent gas barrier properties similar to those under low humidity conditions under high humidity conditions.

Patent Document 2 discloses a film coated with a polyamine and a polycarboxylic acid in a weight ratio of at least one side of a substrate including a plastic film to a polyamine/polycarboxylic acid = 12.5/87.5 to 27.5. Mixture of /72.5 in a way. In the case of the gas barrier film, the gas barrier film is excellent in gas barrier properties, particularly oxygen barrier properties, and is excellent in flexibility, transparency, moisture resistance, chemical resistance, and the like. [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2005-225940 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2013-10857

[Problems to be Solved by the Invention] The gas barrier film described in Patent Document 1 and Patent Document 2 needs to be long at a high temperature in order to crosslink a polycarboxylic acid and a polyamine. Time is heated, so there is still room for improvement in terms of productivity.

The present invention has been made in view of the above-described circumstances, and provides a method for producing a gas barrier layered product having a crosslinked structure of a guanamine formed of a polyamine compound and a polycarboxylic acid, which is excellent in gas barrier performance. [Means for solving the problem]

The inventors of the present invention have repeatedly conducted intensive studies in order to achieve the above problems. As a result, the present invention has been obtained by heating a mixture containing a polycarboxylic acid and a polyamine compound by a specific heating means, whereby the carboxyl group and the polyamine compound contained in the polycarboxylic acid can be efficiently produced. The dehydration condensation reaction of the amine group contained therein makes it possible to efficiently produce a gas barrier layered product having a crosslinked structure of a guanamine formed of a polyamine compound and a polycarboxylic acid, which is excellent in gas barrier properties.

That is, the method for producing a gas barrier layered product shown below is provided by the present invention.

[1] A method for producing a gas barrier layered product, which is a method for producing a gas barrier layered product comprising a base layer and a gas barrier polymer layer provided on at least one of the base layers And comprising: a step of applying a mixture containing a polycarboxylic acid and a polyamine compound onto a substrate layer to obtain a coating layer; and heating the coating layer by a heating mechanism to cause the polycarboxylic acid to be a step of dehydrating condensation reaction of a carboxyl group contained with the amine group contained in the polyamine compound, thereby forming a gas barrier polymer layer having a guanamine bond, and the heating mechanism is selected from a conduction heat transfer method And at least one of radiation heat transfer methods. [2] The method for producing a gas barrier layered product according to the above [1], wherein the heating means comprises at least one selected from the group consisting of conduction heat transfer by a heating roller and radiation heat transfer by infrared rays. [3] The method for producing a gas barrier layered product according to the above [1], wherein the heating means further comprises a convection heat transfer method. [4] The method for producing a gas barrier layered product according to any one of [1] to [3] wherein, in the step of forming the gas barrier polymer layer, heating is performed until the obtained In the infrared absorption spectrum of the gas barrier polymer layer, the total peak area in the range of 1493 cm ^-1 or more and 1780 cm ^-1 or less of the absorption band is A, and the absorption band is 1598 cm ^-1 or more and 1690 cm ^{- When} the total peak area in the range of ¹ or less is B, the area ratio of the indole bond represented by B/A is 0.330 or more. [5] The method for producing a gas barrier layered product according to any one of the above [1], wherein (the -COO- group contained in the polycarboxylic acid in the mixture) Mohr number) / (the number of moles of the amine group contained in the polyamine compound in the mixture) = 100 / more than 22, 100 / 99 or less. [6] The method for producing a gas barrier layered product according to any one of [1] to [5] wherein the polycarboxylic acid comprises a selected from the group consisting of polyacrylic acid, polymethacrylic acid, acrylic acid, and One or two or more polymers of a copolymer of acrylic acid. [7] The method for producing a gas barrier layered product according to any one of the above [1], wherein the polyamine compound contains polyethyleneimine. [Effects of the Invention]

According to the present invention, it is possible to provide a method for producing a gas barrier layered product having a crosslinked structure of a guanamine which is excellent in gas barrier performance and which is formed of a polyamine compound and a polycarboxylic acid.

The above and other objects, features and advantages of the invention will be apparent from the appended claims appended claims

Hereinafter, embodiments of the present invention will be described using the drawings. In addition, the figure is a schematic view and does not coincide with the actual size ratio. In addition, the "~" between the numbers in the text indicates the above to the following unless otherwise specified.

<Manufacturing Method of Gas Blocking Laminate> FIG. 1 and FIG. 2 are cross-sectional views schematically showing an example of the configuration of the gas barrier layered product 100 according to the embodiment of the present invention. The gas barrier layered product 100 includes a base material layer 101 and a mixture of a polycarboxylic acid and a polyamine compound (hereinafter also referred to as a gas barrier coating material) provided on at least one surface of the base material layer 101. A gas barrier polymer layer 103 formed by heating.

Hereinafter, an example of a method of producing the gas barrier layered product 100 of the present embodiment will be described. The method for producing the gas barrier layered product 100 of the present embodiment includes the steps of: (1) applying a mixture containing a polycarboxylic acid and a polyamine compound to the base material layer 101 to obtain a coating layer; and (2) utilizing The heating means heats the coating layer to dehydrate and condense a carboxyl group contained in the polycarboxylic acid with an amine group contained in the polyamine compound, thereby forming a gas barrier property having a guanamine bond The step of polymer layer 103. Further, in the step (2), the heating means contains at least one selected from the group consisting of a conduction heat transfer method and a radiation heat transfer method.

First, the step of (1) applying a mixture containing a polycarboxylic acid and a polyamine compound onto the base material layer 101 to obtain a coating layer will be described.

First, a coating material for gas barrier is prepared. The gas barrier coating material can be produced, for example, as follows.

First, the carboxyl group of the polycarboxylic acid is completely or partially neutralized by adding a base to the polycarboxylic acid. Next, a polyamine compound is added to the polycarboxylic acid in which the carboxyl group is completely or partially neutralized. By mixing the polycarboxylic acid and the polyamine compound in this order, formation of aggregates of the polycarboxylic acid and the polyamine compound can be suppressed, and a uniform gas barrier coating material can be obtained. Thereby, the dehydration condensation reaction of the -COO- group contained in the polycarboxylic acid and the amine group contained in the polyamine compound can be performed more efficiently.

By neutralizing the polycarboxylic acid with the base of the present embodiment, gelation can be suppressed when the polyamine compound is mixed with the polycarboxylic acid. Therefore, in the polycarboxylic acid, from the viewpoint of preventing gelation, it is preferred to form a partial neutralizer or a complete neutralizer of a carboxyl group by a base. The neutralized product can be obtained by partially or completely neutralizing the carboxyl group of the polycarboxylic acid with a base (that is, making the carboxyl group of the polycarboxylic acid partially or completely a carboxylate). Thereby, gelation can be prevented when the polyamine compound is added. Part of the neutralized product can be prepared by adding a base to an aqueous solution of a polycarboxylic acid, and the desired degree of neutralization can be obtained by adjusting the ratio of the amount of the polycarboxylic acid to the base. In the present embodiment, the degree of neutralization of the polycarboxylic acid using the base is preferably from 30 equivalent % to 100 equivalents from the viewpoint of sufficiently suppressing gelation due to neutralization reaction with the amine group of the polyamine compound. % is more preferably 40 equivalent% to 100 equivalent%, still more preferably 50 equivalent% to 100 equivalent%.

As the base, any water-soluble base can be used. Any one or both of a volatile base and a nonvolatile base can be used as the water-soluble base, and it is preferable to be easy to dry and harden from the viewpoint of suppressing a decrease in gas barrier properties due to the remaining free base. The volatile base removed. Examples of the volatile base include tertiary amines such as ammonia, morpholine, alkylamine, 2-dimethylaminoethanol, N-methylmorpholine, ethylenediamine, and triethylamine, or aqueous solutions thereof, or a mixture of these. From the viewpoint of obtaining good gas barrier properties, an aqueous ammonia solution is preferred. Examples of the nonvolatile base include sodium hydroxide, lithium hydroxide, potassium hydroxide or an aqueous solution thereof, or a mixture of these.

In addition, the solid content concentration of the gas barrier coating material is preferably from 0.5% by mass to 15% by mass, and more preferably from 1% by mass to 10% by mass, from the viewpoint of improving the coating property.

(Mixing ratio of polycarboxylic acid and polyamine compound) In the present embodiment, (the number of moles of the -COO- group contained in the polycarboxylic acid in the gas barrier coating material) / (in the gas barrier coating material) The molar number of the amine group contained in the polyamine compound is preferably 100/more than 22, more preferably 100/25 or more, and particularly preferably 100/29 or more. On the other hand, in the present embodiment, (the number of moles of the -COO- group contained in the polycarboxylic acid in the gas barrier coating material) / (the content contained in the polyamine compound in the gas barrier coating material) The molar number of the amine group is preferably 100/99 or less, more preferably 100/86 or less, and particularly preferably 100/75 or less. In order to obtain the gas barrier polymer layer 103 of the present embodiment, it is preferably (the number of moles of the -COO- group contained in the polycarboxylic acid in the gas barrier coating material) / (in the gas barrier coating material) The molar ratio of the amine group contained in the polyamine compound is within the above range, and the blending ratio of the polycarboxylic acid and the polyamine compound in the gas barrier coating material is adjusted.

(Polycarboxylic Acid) The polycarboxylic acid of the present embodiment has two or more carboxyl groups in the molecule. Specific examples thereof include homopolymerization 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 a copolymer of these. Further, it may be a copolymer of the α,β-unsaturated carboxylic acid, an ester such as an ethyl ester, or an olefin such as ethylene. Preferred among these are homopolymers of acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, cinnamic acid or copolymers thereof, more preferably selected from the group consisting of polyacrylic acid, polymethacrylic acid, and acrylic acid. One or two or more polymers of a copolymer with methacrylic acid, further preferably at least one polymer selected from the group consisting of polyacrylic acid and polymethacrylic acid, particularly preferably a homopolymer selected from acrylic acid, methacrylic acid At least one polymer of the homopolymer. Here, in the present embodiment, the polyacrylic acid includes both a homopolymer of acrylic acid and a copolymer of acrylic acid and another monomer. In the case of a copolymer of acrylic acid and another monomer, the polyacrylic acid contains, in 100% by mass of the polymer, usually from 90% by mass or more, preferably 95% by mass or more, more preferably 99% by mass or more, derived from acrylic acid. Structural units. 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, the polymethacrylic acid is contained in a 100% by mass of the polymer, usually 90% by mass or more, preferably 95% by mass or more, and more preferably 99% by mass or more. A structural unit derived from methacrylic acid.

The polycarboxylic acid of the present embodiment is a polymer obtained by polymerizing a carboxylic acid monomer, and the molecular weight of the polycarboxylic acid is preferably from 500 to 2,000,000, more preferably from 1,500 to 5%, from the viewpoint of excellent balance between gas barrier properties and handleability. 1,000,000. Further preferably, it is 5,000 to 500,000, particularly preferably 10,000 to 100,000. 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) The polyamine compound of the present embodiment is a polymer having two or more amine groups in a main chain or a side chain or a terminal. Specific examples thereof include aliphatic polyamines such as polyallylamine, polyvinylamine, polyethyleneimine, and poly(trimethyleneimine); and polyalginic acid and polyarginine have a side chain. Amino-based polyamines and the like. Further, it may be a polyamine which is modified with a part of an amine group. From the viewpoint of obtaining good gas barrier properties, polyethyleneimine is more preferred.

The weight average molecular weight of the polyamine compound of the present embodiment is preferably from 50 to 5,000,000, more preferably from 100 to 2,000,000, still more preferably from 1,500 to 1,000,000, further preferably from the viewpoint of excellent balance between gas barrier properties and handleability. It is 1,500 to 500,000, and particularly preferably 1,500 to 100,000. Here, in the present embodiment, the molecular weight of the polyamine compound can be measured by a boiling point raising method or a viscosity method.

Further, from the viewpoint of preventing shrinkage during coating, it is preferred to further add a surfactant to the gas barrier coating material. When the solid content of the gas barrier coating material is 100% by mass as a whole, the amount of the surfactant added is preferably 0.01% by mass to 3% by mass, and more preferably 0.01% by mass to 1% by mass.

Examples of the surfactant of the present embodiment include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant. From the viewpoint of obtaining good coatability, it is preferably The nonionic surfactant is more preferably a polyoxyalkylene ether.

Examples of the nonionic surfactant include polyoxyalkylene alkyl aryl ethers, polyoxyalkylene alkyl ethers, polyoxyalkylene fatty acid esters, sorbitan fatty acid esters, and fluorenone. It is a surfactant, an acetylene alcohol surfactant, a fluorine-containing surfactant, and the like.

Examples of the polyoxyalkylene alkyl aryl ethers include polyoxyethylidene phenyl ether, polyoxyethyl octyl phenyl ether, and polyoxyethylidene pentyl phenyl ether. Examples of the polyoxyalkylene alkyl ethers include polyoxyethylidene ethers such as polyoxyethylidene ether and polyoxyalkylene lauryl ether. Examples of the polyoxyalkylene fatty acid esters include polyoxyethylene oleate, polyoxyethylidene laurate, and polyoxyethylidene distearate. Examples of the sorbitan fatty acid esters include sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, and polyoxyalkylene. Ethyl monooleate, polyoxyethylidene stearate, and the like. Examples of the anthrone-based surfactant include dimethyl polyoxane and the like. Examples of the ethynyl alcohol-based surfactant include 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 3,6-dimethyl-4-octyne-3,6-. Glycol, 3,5-dimethyl-1-hexyn-3-ol, and the like. Examples of the fluorine-containing surfactant include a fluoroalkyl ester and the like.

The gas barrier coating material of the present embodiment may further contain other additives insofar as the object of the present invention is not impaired. For example, various additives such as a lubricant, a slip agent, an anti-caking agent, an antistatic agent, an antifogging agent, a pigment, a dye, an inorganic or organic filler, and a polyvalent metal compound may be added.

Next, a gas barrier coating material is applied onto the base material layer 101 to obtain a coating layer.

The method of applying the gas barrier coating material of the present embodiment to the base material layer 101 is not particularly limited, and a usual method can be used. For example, a gravure coater such as a Meyer bar coater, an air knife coater, a direct gravure coater, an indirect gravure, an arc gravure coater, a reverse gravure, and a spray nozzle method may be used. Reverse roll coater, five-roll coater, lip coater, bar coating, top feed reverse coater, bottom feed reverse coater and nozzle feed reverse coater A method of coating by various known coaters such as a machine, a reverse bar coater, a die coater, and an applicator.

The thickness (wet thickness) of the coating layer is preferably from 0.05 μm to 300 μm, more preferably from 1 μm to 200 μm, still more preferably from 1 μm to 100 μm, even more preferably from 0.05 μm to 30 μm. When the thickness of the coating layer is at most the above upper limit value, the obtained gas barrier layered product 100 can be suppressed from being curled. In addition, when the thickness of the coating layer is at most the above upper limit value, the dehydration condensation reaction of the -COO- group contained in the polycarboxylic acid with the amine group contained in the polyamine compound can be more effectively performed. Further, when the thickness of the coating layer is at least the lower limit value, the barrier property of the obtained gas barrier layered product 100 can be further improved. The thickness of the gas barrier polymer layer 103 after the heat treatment is preferably from 0.01 μm to 15 μm, more preferably from 0.05 μm to 5 μm, still more preferably from 0.1 μm to 1 μm, from gas barrier properties and to the substrate layer. The stable adhesion balance of 101 is excellent, and it is particularly preferably 0.15 μm to 0.45 μm or less.

Then, (2) heating the coating layer by a heating means to cause a dehydration condensation reaction between a carboxyl group contained in the polycarboxylic acid and an amine group contained in the polyamine compound, thereby forming The step of the gas barrier polymer layer 103 of the guanamine bond will be described.

In the method for producing the gas barrier layered product 100 of the present embodiment, in order to obtain the gas barrier polymer layer 103 of the present embodiment, a "conduction heat transfer method" selected from contact with a high temperature body is used, and utilization is derived from At least one of the "radiation heat transfer method" of the heat radiation of the high temperature body serves as the mechanism for heating the coating layer. Thereby, the dehydration condensation reaction of the carboxyl group contained in the polycarboxylic acid and the amine group contained in the polyamine compound can be efficiently performed.

The conduction heat transfer method is a method of heating a material that is in contact with a high-temperature body by heat conduction, and examples of the apparatus that heats by a conduction heat transfer method include a heat roller. In the case of heating by a heating roller, heating is performed by bringing the heating roller into contact with the material. From the viewpoint of excellent heat transfer efficiency of the film, a heating roll is preferred. The radiation heat transfer method is a method in which the radiation energy of the infrared rays emitted from the high temperature body is used as a heat source, and the infrared rays absorbed by the material become heat in the material to heat the material. As the infrared source, an infrared heater, an infrared lamp, or the like can be used.

In the step of forming the gas barrier polymer layer 103, it is preferred that the heat treatment temperature is 160 ° C to 250 ° C, the heat treatment time is 1 second to 10 minutes, and preferably the heat treatment temperature is 180 ° C to 240 ° C, The heat treatment time is 5 seconds to 5 minutes, more preferably the heat treatment temperature is 190 ° C to 230 ° C, and the heat treatment time is 10 seconds to 2 minutes.

When the coating layer is heated, heating may be performed from the side of the base layer 101, or heating may be performed from the side of the coating layer to obtain a gas barrier polymer layer 103 excellent in gas barrier properties more stably. From the viewpoint of the above, it is preferred to heat from the side of the base material layer 101.

Further, when the coating layer is heated, a heating mechanism using a convection heat transfer method can be suitably combined. Here, the heating by the convection heat transfer method is a heating method using heated air as hot air and directly contacting the material, and the relative speed of the material and the hot air, and the temperature difference between the material and the hot air can be used. The amount of heat transfer caused is controlled. Examples of the apparatus that heats by the convection heat transfer method include a hot air dryer, a hot air oven, a dryer, and the like.

In addition, from the viewpoint of efficiently performing the dehydration condensation reaction of the -COO- group contained in the polycarboxylic acid with the amine group contained in the polyamine compound, it is important to adjust the heat treatment according to the wet thickness of the gas barrier coating material. Temperature and heat treatment time.

In the step of forming the gas barrier polymer layer 103, drying of the coating layer may be performed before the heating of the coating layer. Alternatively, the drying and heat treatment may be simultaneously performed. In the step of forming the gas barrier polymer layer 103, in the case of drying before the heat treatment of the coating layer, it is preferred that the drying temperature is from 60 ° C to 150 ° C and the drying time is from 1 second to 60 seconds. Dry down.

The gas barrier polymer layer 103 of the present embodiment can be formed by the gas barrier coating material, and after the gas barrier coating material is applied onto the base material layer 101 or the inorganic layer 102 to be described later, drying and heat treatment are performed. It is obtained by hardening the gas barrier coating material.

Further, in the step of forming the gas barrier polymer layer 103, heating is performed until the absorption band is in the range of 1493 cm ^-1 or more and 1780 cm ^-1 or less in the infrared absorption spectrum of the obtained gas barrier polymer layer 103. When the total peak area of the absorption band is 1598 cm ^-1 or more and the total peak area of 1690 cm ^-1 or less is B, the area ratio of the indole bond represented by B/A is from gas barrier property. The viewpoint of the viewpoint is preferably 0.330 or more, more preferably 0.370 or more, still more preferably 0.400 or more, and particularly preferably 0.420 or more. Thereby, the gas barrier layered product 100 which is further excellent in gas barrier performance can be obtained. In addition, the upper limit of the area ratio of the amide bond represented by B/A is preferably 0.700 or less, more preferably 0.680 or less, from the viewpoint of further improving the balance of appearance, dimensional stability, and productivity. It is 0.650 or less.

In the infrared absorption spectrum of the gas barrier polymer layer 103 of the present embodiment, absorption of νC=O based on unreacted carboxylic acid is observed in the vicinity of 1700 cm ^-1 , and it is seen in the vicinity of 1630 cm ^-1 to 1685 cm ^-1 . The absorption based on the carboxylate-based νC=O was observed in the vicinity of 1540 cm ^-1 to 1560 cm ^-1 to the absorption of νC=O based on the indole bond of the crosslinked structure. In other words, in the present embodiment, the total peak area A in the range of 1493 cm ^-1 or more and 1780 cm ^-1 or less of the absorption band in the infrared absorption spectrum indicates an index of the total amount of the carboxylic acid and the guanamine bond and the carboxylate. The total peak area B in the range of 1598 cm ^-1 or more and 1690 cm ^-1 or less of the absorption band indicates the index of the amount of the guanamine bond, and the total range of the absorption band of 1690 cm ^-1 or more and 1780 cm ^-1 or less which will be described later. The peak area C indicates an index of the amount of the unreacted carboxylic acid, and the total peak area D in the range of 1493 cm ^-1 or more and 1598 cm ^-1 or less of the absorption band to be described later indicates a carboxylate, that is, a carboxyl group and an amine group. An indicator of the amount of cross-linking present.

Further, in the present embodiment, the total peak area A to the total peak area D can be measured by the following procedure. First, a measurement sample of 1 cm × 3 cm was cut out from the gas barrier polymer layer 103 of the present embodiment. Next, an infrared absorption spectrum of the surface of the gas barrier polymer layer 103 is obtained by an infrared total reflection measurement (ATR (Attenuated Total Reflection) method). The total peak area A to the total peak area D were calculated from the obtained infrared absorption spectrum by the following procedures (1) to (4). (1) The absorbance at 1780 cm ^-1 and 1493 cm ^-1 is connected by a straight line (N), and the absorption spectrum of the absorption band of 1493 cm ^-1 or more and 1780 cm ^-1 or less and the area surrounded by N are taken as the total peak area. A. (2) A straight line (O) is drawn vertically from the absorbance (Q) of 1690 cm ^-1 , and the intersection of N and O is taken as P, and the straight line (S) is drawn vertically from the absorbance (R) of 1598 cm ^-1 . The intersection of N and S is T, and the absorption spectrum of the absorption band of 1598 cm ^-1 or more and 1690 cm ^-1 or less and the straight line S, the point T, the straight line N, the point P, the straight line O, the absorbance Q, and the absorbance. The area surrounded by R is taken as the total peak area B. (3) The absorption spectrum of the absorption band of 1690 cm ^-1 or more and 1780 cm ^-1 or less and the area surrounded by the absorbance Q, the straight line O, the point P, and the straight line N are taken as the total peak area C. (4) The absorption spectrum of the absorption band of 1493 cm ^-1 or more and 1598 cm ^-1 or less and the area surrounded by the absorbance R, the straight line S, the point T, and the straight line N are taken as the total peak area D. Next, the area ratios B/A, C/A, and D/A were obtained from the areas obtained by the above method. In the measurement of the infrared absorption spectrum (infrared total reflection measurement: ATR method) of the present embodiment, for example, an IRT-5200 device manufactured by JASCO Corporation can be used, and PKM-GE-S (Germanium) crystals can be attached at an incident angle. It was carried out under the conditions of 45 degrees, room temperature, resolution of 4 cm ^-1 , and cumulative number of times of 100 times.

In the gas barrier polymer layer 103 formed of a mixture containing a polycarboxylic acid and a polyamine compound, there are two kinds of crosslinked structures in which ionic crosslinking and guanamine are crosslinked, and the crosslinked structures are present in a gas barrier property. It is important to raise the point of view. In addition, the ionic cross-linking is produced by an acid-base reaction of a carboxyl group contained in a polycarboxylic acid with an amine group contained in a polyamine compound, and the cross-linking of the guanamine means a polycarboxylic acid. The carboxyl group contained in the molecule and the amine group contained in the polyamine compound are produced by a dehydration condensation reaction. Therefore, it is used to improve the gas barrier properties such as oxygen barrier properties and water vapor barrier properties under high humidity and after boiling and retort treatment, and to improve the balance of appearance, dimensional stability, and productivity. The design guidelines can be applied to the scale of the area ratio of the indole bond represented by the B/A. By controlling the manufacturing conditions, the area ratio of the indole bond represented by the B/A of the gas barrier polymer layer 103 can be adjusted to a specific value or more, and the gas barrier polymer layer 103 having such characteristics can be obtained. The gas barrier properties under both conditions of high humidity and boiling and retort treatment are more effectively exhibited, and the balance of appearance, dimensional stability, and productivity is also excellent. In other words, by setting the area ratio of the indole bond represented by B/A to the lower limit or more, oxygen barrier properties and water under both conditions of high humidity and boiling and retort treatment can be obtained. The gas barrier layered product 100 is further excellent in vapor barrier properties and excellent in balance of appearance, dimensional stability, and productivity.

The reason why the performance balance of the gas barrier polymer layer 103 is excellent is not necessarily clear, and it is considered that the reason is that the area ratio of the guanamine bond represented by B/A is a gas barrier polymer layer within the above range. The ionic cross-linking and guanamine cross-linking of the two cross-linking structures form a dense structure in a well-balanced manner. That is, the area ratio of the indole bond represented by the B/A is within the range, indicating that the two crosslinked structures can be formed in a well-balanced manner by ion crosslinking and guanamine crosslinking.

Further, in the step of forming the gas barrier polymer layer 103, heating is performed until the absorption band is in the range of 1690 cm ^-1 or more and 1780 cm ^-1 or less in the infrared absorption spectrum of the obtained gas barrier polymer layer 103. When the total peak area is set to C, the area ratio of the carboxylic acid represented by C/A is preferably 0.040 or more, and more preferably 0.060 or more from the viewpoint of further improving the balance of appearance, dimensional stability, and productivity. Very good for 0.080 or more. Furthermore, the upper limit of the area ratio of the carboxylic acid represented by the C/A is considered from the viewpoint of further improving the oxygen barrier property and the water vapor barrier property under the two conditions of high humidity and boiling and retort treatment. It is preferably 0.500 or less, more preferably 0.450 or less, and particularly preferably 0.400 or less.

Further, in the step of forming the gas barrier polymer layer 103, heating is performed until the absorption band is in the range of 1493 cm ^-1 or more and 1598 cm ^-1 or less in the infrared absorption spectrum of the obtained gas barrier polymer layer 103. When the total peak area is set to D, the carboxylic acid represented by D/A is considered from the viewpoint of further improving oxygen barrier properties and water vapor barrier properties under high humidity and after boiling and retort treatment. The area ratio of the salt is preferably 0.100 or more, more preferably 0.150 or more. In addition, the upper limit of the area ratio of the carboxylate represented by the D/A is preferably 0.450 or less, more preferably 0.420 or less, from the viewpoint of further improving the balance of appearance, dimensional stability, and productivity. It is 0.400 or less.

The area ratio of the indole bond represented by B/A of the gas barrier polymer layer 103 of the present embodiment, the area ratio of the carboxylic acid represented by C/A, and the area ratio of the carboxylate represented by D/A may be It is controlled by appropriately adjusting the manufacturing conditions of the gas barrier polymer layer 103. In the present embodiment, in particular, a compounding ratio of a polycarboxylic acid and a polyamine compound, a method for preparing a gas barrier coating material, a method of heat treatment of the gas barrier coating material, temperature, time, and the like are used as a control unit. The area ratio of the indole bond represented by B/A, the area ratio of the carboxylic acid represented by the C/A, and the area ratio of the carboxylate represented by the D/A are listed.

(Base Material Layer) The base material layer 101 of the present embodiment may be 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 the group consisting of a thermosetting resin and a thermoplastic resin.

The thermosetting resin may, for example, be a known thermosetting resin such as an epoxy resin, an unsaturated polyester resin, a phenol resin, a urea-melamine resin, a polyurethane resin, an anthrone resin, a polyimine or the like.

The thermoplastic resin may, for example, be a known thermoplastic resin such as polyolefin (polyethylene, polypropylene, poly(4-methyl-1-pentene), poly(1-butene), etc.), polyester (polyterephthalic acid). Ethylene glycol ester, polybutylene terephthalate, polyethylene naphthalate, etc.), polydecylamine (nylon-6, nylon-66, polyxamethylenedimethylenediamine, etc.), polyvinyl chloride Polyimine, ethylene-vinyl acetate copolymer or saponified product thereof, polyvinyl alcohol, polyacrylonitrile, polycarbonate, polystyrene, ionic polymer, fluororesin or a mixture thereof. Among these, from the viewpoint of good transparency, it is preferably selected from the group consisting of polypropylene, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, and polydecylamine. One or two or more kinds of polyimine, more preferably one or more selected from the group consisting of polyethylene terephthalate and polyethylene naphthalate. Further, the base material layer 101 formed of a thermoplastic resin may be a single layer or two or more layers depending on the use of the gas barrier layered product 100.

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

The base material layer 101 of the present embodiment is preferably selected from the group consisting of polypropylene, polyethylene terephthalate, and polybutylene terephthalate from the viewpoint of excellent transparency, rigidity, and heat resistance. a biaxially stretched film formed of one or two or more thermoplastic resins of polyethylene naphthalate, polyamidamine or polyimine, more preferably selected from the group consisting of polyethylene terephthalate and polynaphthalene A biaxially stretched film formed of one or two or more thermoplastic resins of ethylene formate.

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

The thickness of the base material layer 101 is preferably from 1 μm to 1000 μm, more preferably from 1 μm to 500 μm, still more preferably from 1 μm 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 a film shape, a shape such as a disk, a cup, and a hollow body.

(Inorganic Layer) As shown in FIG. 2, in the gas barrier layered product 100, the inorganic layer 102 may be further laminated between the base layer 101 and the gas barrier polymer layer 103. Thereby, the barrier property such as oxygen barrier property or water vapor barrier property can be further improved.

The inorganic material constituting the inorganic material layer 102 of the present embodiment may, for example, be a metal, a metal oxide, a metal nitride, a metal fluoride, a metal oxynitride or the like which can form a barrier film. Examples of the inorganic material constituting the inorganic layer 102 include a periodic table 2A element selected from the group consisting of strontium, magnesium, calcium, strontium, barium, and the periodic table transition elements such as titanium, zirconium, hafnium, tantalum, and lanthanum; and Group 2B elements of the periodic table such as zinc; Elements of Group 3A of the periodic table such as aluminum, gallium, indium and antimony; elements of Group 4A of the periodic table such as lanthanum, cerium and tin; elemental, oxide, nitride, fluoride or nitrogen of elements such as selenium and tellurium One or two or more kinds of oxides. Further, in the present embodiment, the family name of the periodic table is represented by the old CAS formula.

In addition, in the inorganic material, it is preferably one or two or more inorganic materials selected from the group consisting of cerium oxide, aluminum oxide, and aluminum, in view of excellent balance between barrier properties and cost. Further, in the cerium oxide, in addition to cerium oxide, cerium oxide or cerium oxide may be contained.

The inorganic layer 102 is composed of the inorganic substance. The inorganic layer 102 may be composed of a single layer of an inorganic layer or a plurality of inorganic layers. Further, when the inorganic material layer 102 is composed of a plurality of inorganic material layers, it may be composed of the same type of inorganic material layer or may be composed of different types of inorganic material 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 balance between barrier properties, adhesion, and workability. In the present embodiment, the thickness of the inorganic layer 102 can be obtained by using an observation image of a transmission electron microscope or a scanning electron microscope.

The method for forming the inorganic layer 102 is not particularly limited, and may be, for example, a vacuum deposition method, an ion plating method, a sputtering method, a chemical vapor deposition method, a physical vapor deposition method, or a chemical vapor deposition method (CVD ( The inorganic layer 102 is formed on one or both sides of the base material layer 101 by a chemical vapor CVD method, a sol-gel method, or the like. Among them, sputtering, ion plating, chemical vapor deposition (CVD), physical vapor deposition (PVD (Physical Vapor Deposition)), plasma CVD, etc., are preferably performed under reduced pressure. . Thereby, the chemically active molecular species containing cerium such as cerium nitride or cerium oxynitride are rapidly reacted, whereby the smoothness of the surface of the inorganic layer 102 is improved, and the number of pores can be reduced. When these binding reactions are carried out rapidly, it is desirable that the inorganic atom or compound be a chemically active molecular species or atomic species.

The gas barrier layered product 100 of the present embodiment is excellent in gas barrier performance, and can be used as a packaging material, particularly a food packaging material requiring a high gas barrier property, medical use, industrial use, and daily grocery use. Suitable for packaging materials. In addition, the gas barrier layered product 100 of the present embodiment can be suitably used as a film for vacuum heat insulation which requires high barrier performance, and is used for sealing a film for sealing such as an electroluminescent element or a solar cell.

Although the embodiments of the present invention have been described above with reference to the drawings, these are examples of the invention, and various configurations other than the above may be employed. [Examples]

Hereinafter, the present embodiment will be described in detail with reference to examples and comparative examples. Further, the present embodiment is not limited to the description of the embodiments.

<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% by mass aqueous solution, molecular weight: 100,000). A 10% by mass solution of an aqueous solution of ammonium polyacrylate. <Preparation of Solution (Y)> Purified water was added to a polyethyleneimine (manufactured by Wako Pure Chemical Industries, Ltd., product name: polyethyleneimine, average molecular weight: about 10,000) to obtain a 10% by mass solution. An aqueous solution of polyethyleneimine.

[Example 1-1] 79 g of the aqueous ammonium polyacrylate solution (Z) and 21 g of the aqueous polyethyleneimine solution (Y) were mixed and stirred to prepare a mixed solution. Further, the purified water is added so that the solid content concentration of the mixed liquid is 2.5% by mass, and the mixture is stirred until it becomes a homogeneous solution, and then the nonionic interface activity is mixed so as to be 0.3% by mass based on the solid content of the mixed liquid. A solution (polyoxyethylene ethyl lauryl ether, manufactured by Kao Corporation, trade name: EMULGEN 120) was prepared to prepare a solution (V). The obtained solution (V) was applied to a biaxial layer having a thickness of 12 μm by a Mayer bar having a thickness after heat treatment (that is, a film thickness of the gas barrier polymer layer) of 0.3 μm. A corona-treated surface of a polyethylene terephthalate film (manufactured by Unitika Co., Ltd., PET12) was used, and dried using a hot air dryer at a temperature of 100 ° C for 30 seconds. The gas barrier layered film was obtained by heat treatment under the conditions of a temperature of 200 ° C and a time of 60 seconds by a hot roll.

[Example 1-2] A gas barrier laminated film was obtained in the same manner as in Example 1-1, except that the heat roller was used in combination with a far-infrared heater and a hot air dryer.

[Comparative Example 1] A gas barrier laminated film was obtained in the same manner as in Example 1-1, except that the hot roll was used as a hot air dryer.

[Example 2-1] A gas barrier laminated film was obtained in the same manner as in Example 1-1 except that the heat treatment was carried out under the conditions of a temperature of 210 ° C and a time of 60 seconds.

[Example 2-2] A gas barrier laminated film was obtained in the same manner as in Example 2-1, except that the heat roller was used in combination with a far-infrared heater and a hot air dryer.

[Comparative Example 2] A gas barrier laminated film was obtained in the same manner as in Example 2-1, except that the hot roll was used as a hot air dryer.

[Example 3] A gas barrier laminated film was obtained in the same manner as in Example 1-1, except that the heat treatment was carried out under the conditions of a temperature of 220 ° C and a time of 45 seconds.

[Comparative Example 3] A gas barrier laminated film was obtained in the same manner as in Example 3 except that the hot roll was used as a hot air dryer.

The gas barrier laminated film obtained in the examples and the comparative examples was subjected to the following evaluation. The results obtained are shown in Table 1.

<Preparation of multilayer film for physical property evaluation> (1) One-side coating of an unstretched polypropylene film (manufactured by Mitsui Chemicals Tohcello Co., Ltd., trade name: RXC-22) having a thickness of 70 μm Adhesive (polyurethane-based adhesive (manufactured by Mitsui Chemicals, Inc., trade name: Takelac A525S): 9 parts by mass, isocyanate-based hardener (manufactured by Mitsui Chemicals, Inc., trade name: tower) Takenate A50): 1 part by mass and ethyl acetate: 7.5 parts by mass). After drying, the gas barrier polymer layer of the gas barrier laminated film obtained in the examples and the comparative examples was laminated (dry lamination) to obtain a multilayer film.

(2) Digestion treatment The multilayer film obtained in the above (1) was folded so that the unstretched polypropylene film became the inner surface, and both sides were heat-sealed to form a bag shape, and then 70 cc of water was placed as a content. The bag was made by heat-sealing the other side, and it was subjected to a retort treatment in a high-temperature autoclave sterilization apparatus at 130 ° C for 30 minutes. After the retort treatment, the water of the contents was removed to obtain a multilayer film after the retort treatment.

(3) Oxygen permeability [ml/(m ² ·day·MPa)] OX-TRAN 2/21 manufactured by Mocon Co., Ltd. was used according to JIS K 7126 at a temperature of 20 ° C and a humidity of 90% RH. The multilayer film obtained by the above method was measured.

(4) Measurement of IR area ratio infrared absorption spectrum (infrared total reflection measurement: ATR method) is an IRT-5200 apparatus manufactured by JASCO Corporation, and PKM-GE-S (Germanium) crystal is installed at an incident angle of The measurement was carried out under the conditions of 45 degrees, room temperature, resolution of 4 cm ^-1 , and cumulative number of times of 100 times. The obtained absorption spectrum was analyzed by the above method to calculate the total peak area A to the total peak area D. Then, the area ratio B/A, the area ratio C/A, and the area ratio D/A were obtained from the total peak area A to the total peak area D.

[Table 1] Table 1

When Example 1-1, Example 1-2, and Comparative Example 1 in which the heat treatment time and temperature were the same were compared, the guanamine of Example 1-1 and Example 1-2 heated by a hot roll or far infrared ray was used. The ratio of the bond (B/A) was larger than that of Comparative Example 1 using only a hot air dryer as a heating mechanism of the coating layer. That is, it was found that Example 1-1 and Example 1-2 were able to produce the gas barrier polymer layer 103 having a guanamine crosslinked structure more efficiently than Comparative Example 1. Further, it has been found that such a gas barrier laminated film has a low oxygen permeability and is excellent in gas barrier properties. Further, according to the comparative examples of Example 2-1, Example 2-2 and Comparative Example 2 in which the heat treatment time and temperature were the same, or the comparative examples of Example 3 and Comparative Example 3, it was found that the heat roller or far infrared ray heating was used. The ratio of the guanamine bond (B/A) of the examples was more than that of the comparative example using only the hot air dryer as the heating means of the coating layer. As described above, the gas barrier layered product excellent in gas barrier performance can be efficiently produced by the production method of the present invention.

The present application claims priority on the basis of Japanese Patent Application No. 2015-103500, filed on May 21, 2015, the content of which is hereby incorporated by reference.

100‧‧‧ gas barrier laminate
101‧‧‧Substrate layer
102‧‧‧Inorganic layer
103‧‧‧ gas barrier polymer layer

FIG. 1 is a cross-sectional view showing an example of a structure of a gas barrier layered product according to an embodiment of the present invention. FIG. 2 is a cross-sectional view showing an example of a configuration of a gas barrier layered product according to an embodiment of the present invention.

100‧‧‧ gas barrier laminate

101‧‧‧Substrate layer

103‧‧‧ gas barrier polymer layer

Claims (7)

A method for producing a gas barrier layered product, which is a method for producing a gas barrier layered product comprising a base layer and a gas barrier polymer layer provided on at least one of the base layer, and includes : a step of applying a mixture containing a polycarboxylic acid and a polyamine compound onto a substrate layer to obtain a coating layer; and heating the coating layer by a heating means to include the polycarboxylic acid a step of dehydrating condensation reaction of a carboxyl group with an amine group contained in the polyamine compound, thereby forming a gas barrier polymer layer having a guanamine bond, and the heating mechanism contains a method selected from a conduction heat transfer method and radiation transmission At least one of the hot ways. The method for producing a gas barrier layered product according to the first aspect of the invention, wherein the heating means comprises at least one selected from the group consisting of conduction heat transfer by a heating roller and radiation heat transfer by infrared rays. The method for producing a gas barrier layered product according to the above aspect of the invention, wherein the heating means further comprises a convection heat transfer method. The method for producing a gas barrier layered product according to the above aspect, wherein the step of forming the gas barrier polymer layer is performed until the gas barrier polymerization is obtained. In the infrared absorption spectrum of the layer, the total peak area in the range of 1493 cm ^-1 or more and 1780 cm ^-1 or less of the absorption band is A, and the total band of the absorption band is 1598 cm ^-1 or more and 1690 cm ^-1 or less. When the peak area is B, the area ratio of the indole bond represented by B/A is 0.330 or more. The method for producing a gas barrier layered product according to the above aspect, wherein (the number of moles of the -COO- group contained in the polycarboxylic acid in the mixture) is / (The number of moles of the amine group contained in the polyamine compound in the mixture) = 100 / more than 22, 100 / 99 or less. The method for producing a gas barrier layered product according to the above aspect, wherein the polycarboxylic acid comprises a copolymer selected from the group consisting of polyacrylic acid, polymethacrylic acid, and a copolymer of acrylic acid and methacrylic acid. One or two or more polymers. The method for producing a gas barrier layered product according to the above aspect, wherein the polyamine compound contains polyethyleneimine.