TWI692495B - Method for producing gas-barrier laminate - Google Patents

Abstract

The manufacturing method of the gas barrier laminate (100) of the present invention is a gas including a base layer (101) and a gas barrier polymer layer (103) provided on at least one surface of the base layer (101) A method for manufacturing a barrier layered product (100), comprising: a step of applying a mixture containing a polycarboxylic acid and a polyamine compound on a substrate layer (101) to obtain a coating layer; The coating layer is heated to cause a dehydration condensation reaction between the carboxyl group contained in the polycarboxylic acid and the amine group contained in the polyamine compound, thereby forming a gas barrier polymer layer having an amide bond (103 )A step of. In addition, the heating mechanism includes at least one selected from a conductive heat transfer method and a radiant heat transfer method.

Description

Manufacturing method of gas-barrier laminate

The invention relates to a method for manufacturing a gas-barrier laminate.

In general, as the gas barrier material, a laminate in which an inorganic layer as a gas barrier layer is provided on the base material layer is used.

However, the inorganic layer is not resistant to rubbing, etc., such a gas-barrier laminate has cracks in the inorganic layer due to friction or elongation during printing, lamination of the post-processing, or filling of contents, resulting in gas barrier properties Reduced phenomenon.

Therefore, the gas barrier material also uses a laminate in which an organic substance layer is used as the gas barrier layer.

As for a gas barrier material using an organic substance 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.

Examples of technologies related to such gas barrier laminates include those described in Patent Document 1 (Japanese Patent Laid-Open No. 2005-225940) and Patent Document 2 (Japanese Patent Laid-Open No. 2013-10857). .

Patent Document 1 discloses a gas barrier film including 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 40% or more.

Patent Document 1 describes that such a gas barrier film also has the same excellent gas barrier properties as under low humidity conditions under high humidity conditions.

Patent Document 2 discloses a film coated with polyamine and polycarboxylic acid at a weight ratio of at least one side of a substrate including a plastic film to become polyamine/polycarboxylic acid=12.5/87.5~27.5 /72.5 mixture.

Patent Document 2 describes that such a gas barrier film has excellent gas barrier properties, especially oxygen barrier properties even after boiling treatment, and is excellent in flexibility, transparency, moisture resistance, chemical resistance, and the like.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2005-225940

[Patent Document 2] Japanese Patent Laid-Open No. 2013-10857

According to studies by the present inventors and others, it is known that the gas barrier films described in Patent Document 1 and Patent Document 2 need to be heated at a high temperature for a long period of time in order to crosslink the polycarboxylic acid and the polyamine. Therefore, in terms of productivity There is still room for improvement.

The present invention has been made in view of the above facts, and provides a method for efficiently manufacturing a gas-barrier laminate having an amide cross-linked structure formed of a polyamine compound and a polycarboxylic acid, which is excellent in gas barrier performance.

In order to achieve the above-mentioned problems, the inventors of the present invention have repeatedly conducted keen research. As a result, the following findings have been made to complete the present invention: a specific heating mechanism is used to heat a mixture containing a polycarboxylic acid and a polyamine compound, 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 in it efficiently produces a gas-barrier laminate having an amide cross-linked structure formed of a polyamine compound and a polycarboxylic acid, which is excellent in gas barrier performance.

That is, the present invention provides a method for manufacturing the gas barrier laminate shown below.

[1]

A method for manufacturing a gas-barrier laminate, which is a method for manufacturing a gas-barrier laminate including a substrate layer and a gas-barrier polymer layer provided on at least one surface of the substrate layer, and includes : A step of applying a mixture containing a polycarboxylic acid and a polyamine compound on a substrate layer to obtain a coating layer; and heating the coating layer by a heating mechanism to make the polycarboxylic acid contained in the coating layer The carboxyl group undergoes a dehydration condensation reaction with the amine group contained in the polyamine compound, thereby forming a step of forming a gas-barrier polymer layer having an amide bond, and the heating mechanism includes a method selected from conductive heat transfer and radiation transfer At least one of the thermal methods.

[2]

The method for manufacturing a gas-barrier laminate according to [1] above, wherein the heating mechanism includes a heat transfer selected from conductive heat transfer using a heating roller and infrared radiation transfer At least one kind of heat.

[3]

The method for manufacturing a gas-barrier laminate according to [1] or [2], wherein the heating mechanism further includes a convection heat transfer method.

[4]

The method for producing a gas-barrier laminate according to any one of [1] to [3], wherein in the step of forming the gas-barrier polymer layer, heating is performed until the resulting gas infrared absorption spectrum of the polymer barrier layer, the absorption band 1493cm ^-1 or more, and the total peak area in the range 1780cm ^-1 or less is a, the above absorption band 1598cm ^-1, 1690cm ^-1 total peak range below When the area is B, the area ratio of the amide bond represented by B/A is 0.330 or more.

[5]

The method for producing a gas-barrier laminate according to any one of [1] to [4], wherein (the -COO-based mole contained in the polycarboxylic acid in the mixture Number)/(mole number of amine groups contained in the polyamine compound in the mixture)=100/(over 22), 100/(99 or less).

[6]

The method for producing a gas-barrier laminate according to any one of [1] to [5], wherein the polycarboxylic acid contains a polyacrylic acid, polymethacrylic acid, or propylene One or two or more polymers of a copolymer of acid and methacrylic acid.

[7]

The method for producing a gas-barrier laminate according to any one of [1] to [6], wherein the polyamine compound contains polyethyleneimine.

The present invention can provide a method for efficiently manufacturing a gas-barrier laminate having an amide cross-linked structure formed of a polyamine compound and a polycarboxylic acid and having excellent gas barrier performance.

The above object, and other objects, features, and advantages will be further clarified by the appropriate embodiments described below and the following drawings accompanying them.

100: gas barrier laminate

101: substrate layer

102: inorganic layer

103: gas barrier polymer layer

FIG. 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.

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

Hereinafter, embodiments of the present invention will be described using drawings. In addition, the figure is a schematic diagram and does not match the actual size ratio. In addition, "~" between numbers in the text means from above to below unless otherwise specified.

<Manufacturing method of gas barrier laminate>

1 and 2 are diagrams schematically showing gas barrier properties of an embodiment of the present invention A cross-sectional view of an example of the structure of the layer body 100.

The gas-barrier laminate 100 includes a base material layer 101 and a coating material for a gas barrier provided on at least one surface of the base material layer 101 by a mixture containing a polycarboxylic acid and a polyamine compound (hereinafter also referred to as a gas barrier) ) The gas barrier polymer layer 103 formed by heating.

Hereinafter, an example of the method for manufacturing the gas barrier laminate 100 of the present embodiment will be described.

The manufacturing method of the gas-barrier laminate 100 of this embodiment includes: (1) a step of applying a mixture containing a polycarboxylic acid and a polyamine compound on a base material layer 101 to obtain a coating layer; and (2) using The heating mechanism heats the coating layer to cause a dehydration condensation reaction between the carboxyl group contained in the polycarboxylic acid and the amine group contained in the polyamine compound, thereby forming a gas barrier property having an amide bond Step of the polymer layer 103. Furthermore, in the step (2), the heating mechanism includes at least one selected from a conductive heat transfer method and a radiant heat transfer method.

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

First, a coating material for gas barrier is prepared.

The coating material for gas barrier can be prepared as follows, for example.

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, the formation of aggregates of the polycarboxylic acid and the polyamine compound can be suppressed, and a uniform gas barrier coating can be obtained material. 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 using the base of the present embodiment, gelation can be suppressed when the polyamine compound and the polycarboxylic acid are mixed. Therefore, from the viewpoint of preventing gelation among the polycarboxylic acids, it is preferable to partially or completely neutralize the carboxyl group made of 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). This can prevent gelation when the polyamine compound is added.

The partially neutralized product can be prepared by adding an alkali to an aqueous solution of polycarboxylic acid, and by adjusting the amount ratio of polycarboxylic acid to alkali, a desired degree of neutralization can be obtained. In the present embodiment, from the viewpoint of sufficiently suppressing gelation caused by the neutralization reaction with the amine group of the polyamine compound, the degree of neutralization of the polycarboxylic acid with an alkali is preferably 30 equivalent% to 100 equivalents %, more preferably 40 equivalent% to 100 equivalent%, and even more preferably 50 equivalent% to 100 equivalent%.

As the base, any water-soluble base can be used. As the water-soluble base, either or both of the volatile base and the non-volatile base can be used. From the viewpoint of suppressing the reduction of the gas barrier property caused by the remaining free base, it is preferable that it can be easily dried or hardened. Volatile bases.

Examples of volatile bases include tertiary amines such as ammonia, morpholine, alkylamines, 2-dimethylaminoethanol, N-methylmorpholine, ethylenediamine, and triethylamine, or aqueous solutions of these, or these Some mixture. From the viewpoint of obtaining good gas barrier properties, an aqueous ammonia solution is preferred.

Examples of non-volatile bases include sodium hydroxide, lithium hydroxide, potassium hydroxide, or aqueous solutions of these, or mixtures of these.

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

(Proportioning ratio of polycarboxylic acid and polyamine compound)

In this embodiment, (the number of moles of -COO- group contained in the polycarboxylic acid in the coating material for gas barrier)/(the mole of the amine group contained in the polyamine compound in the coating material for gas barrier) The number of ears) is preferably 100/(over 22), more preferably 100/(over 25), and particularly preferably 100/(over 29).

On the other hand, in this embodiment, (the number of moles of -COO- group contained in the polycarboxylic acid in the coating material for gas barrier)/(the content in the polyamine compound in the coating material for gas barrier The mole number of amine groups) 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 preferable to use (the number of moles of -COO- group contained in the polycarboxylic acid in the coating material for gas barrier)/(in the coating material for gas barrier The number of moles of amine groups contained in the polyamine compound of) is within the above range, and the blending ratio of the polycarboxylic acid and the polyamine compound in the coating material for gas barrier is adjusted.

(Polycarboxylic acid)

The polycarboxylic acid of this embodiment has two or more carboxyl groups in the molecule. Specific examples 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-hexenoic acid. Thing or something Copolymer. Moreover, it may be a copolymer of the above-mentioned α,β-unsaturated carboxylic acid, esters such as ethyl ester, and olefins such as ethylene.

Among these, homopolymers or copolymers of acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, and cinnamic acid are preferred, and more preferably selected from 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 polyacrylic acid and polymethacrylic acid, particularly preferably a homopolymer selected from acrylic acid, methacrylic acid At least one polymer.

Here, in the present embodiment, the polyacrylic acid includes both a homopolymer of acrylic acid and a copolymer of acrylic acid and other monomers. In the case of a copolymer of acrylic acid and other monomers, polyacrylic acid usually contains 90% by mass or more, preferably 95% by mass or more, and more preferably 99% by mass or more of acrylic acid-derived in 100% by mass of the polymer. Structural units.

Furthermore, in the present embodiment, the 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 is contained in 100% by mass of the polymer, usually 90% by mass or more, preferably 95% by mass or more, more preferably 99% by mass or more Structural unit derived from methacrylic acid.

The polycarboxylic acid of the present embodiment is a polymer obtained by polymerizing carboxylic acid monomers. From the viewpoint of excellent balance between gas barrier properties and operability, the molecular weight of the polycarboxylic acid is preferably 500 to 2,000,000, more preferably 1,500 to 1,000,000. Further, it is preferably 5,000 to 500,000, and particularly preferably 10,000 to 100,000.

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 (Gel Permeation Chromatography, GPC).

(Polyamine compound)

The polyamine compound of this embodiment is a polymer having two or more amine groups in the main chain, side chain, or terminal. Specific examples include aliphatic polyamines such as polyallylamine, polyvinylamine, polyethyleneimine, and poly(trimethyleneimine); such as polyimide and polyspermine, which have side chains Amine-based polyamides, etc. Furthermore, it may be a polyamine that modifies a part of the amine group. From the viewpoint of obtaining good gas barrier properties, polyethyleneimine is more preferable.

From the viewpoint of excellent balance between gas barrier properties and operability, the weight average molecular weight of the polyamine compound of this embodiment is preferably 50 to 5,000,000, more preferably 100 to 2,000,000, still more preferably 1,500 to 1,000,000, and still more preferably It's 1,500~500,000, especially 1,500~100,000.

Here, in this embodiment, the molecular weight of the polyamine compound can be measured using a boiling point increase method or a viscosity method.

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

Examples of the surfactant of the present embodiment include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric interfaces. From the viewpoint of obtaining good coatability, the active agent and the like are preferably nonionic surfactants, and more preferably polyoxyethylene alkyl ethers.

Examples of nonionic surfactants include polyoxyalkylene alkyl aryl ethers, polyoxyalkylene alkyl ethers, polyoxyalkylene fatty acid esters, sorbitan fatty acid esters, and silicones. Surfactants, acetylene alcohol surfactants, fluorine-containing surfactants, etc.

Examples of the polyoxyalkylene alkyl aryl ethers include polyoxyethyl ethyl nonyl phenyl ether, polyoxy ethyl octyl phenyl ether, and polyoxy ethyl dodecyl phenyl ether.

Examples of the polyoxyalkylene alkyl ethers include polyoxyethylene alkyl ethers such as polyoxyethyl oleyl ether and polyoxyethyl lauryl ether.

Examples of the polyoxyalkylene fatty acid esters include polyoxyethylidene oleate, polyoxyethylidene laurate, and polyoxyethylidene distearate.

Examples of sorbitan fatty acid esters include sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, and polyoxyalkylene. Ethyl monooleate, polyoxyethyl stearate, etc.

Examples of silicone-based surfactants include dimethyl polysiloxane.

Examples of acetylene alcohol-based surfactants include 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 3,6-dimethyl-4-octyne-3,6- Diol, 3,5-dimethyl-1-hexyn-3-ol, etc.

Examples of fluorine-containing surfactants include fluoroalkyl esters.

The coating material for gas barrier of the present embodiment may further contain other additives within a range that does not impair the object of the present invention. For example, lubricants can also be added Various additives such as slip agents, anti-caking agents, antistatic agents, anti-fogging agents, pigments, dyes, inorganic or organic fillers, polyvalent metal compounds, etc.

Next, the coating material for gas barrier is coated on the base material layer 101 to obtain a coating layer.

The method of applying the coating material for gas barrier of the present embodiment on the base material layer 101 is not particularly limited, and a general method can be used. For example, a gravure coater using a meyer bar coater, an air knife coater, a direct gravure coater, an indirect gravure, an arc gravure coater, a reverse gravure, and a jet nozzle method, etc. Reverse roll coater such as top feed reverse coater, bottom feed reverse coater and nozzle feed reverse coater, five roll coater, die lip coater, bar coater Coating method using various well-known coating machines such as machine, reverse bar coater, die coater, applicator and the like.

The thickness (wet thickness) of the coating layer is preferably 0.05 μm to 300 μm, more preferably 1 μm to 200 μm, still more preferably 1 μm to 100 μm, and particularly preferably 0.05 μm to 30 μm.

If the thickness of the coating layer is equal to or less than the upper limit value, curling of the obtained gas barrier laminate 100 can be suppressed. In addition, if the thickness of the coating layer is equal to or less than the upper limit value, the dehydration condensation reaction of the -COO- group contained in the polycarboxylic acid and the amine group contained in the polyamine compound can be more efficiently performed.

In addition, if the thickness of the coating layer is equal to or greater than the above lower limit, the barrier performance of the resulting gas barrier laminate 100 can be further improved.

The thickness of the gas barrier polymer layer 103 after heat treatment is preferably 0.01 μm to 15 μm, more preferably 0.05 μm to 5 μm, and still more preferably 0.1 μm to 1 μm. In consideration of the balance between gas barrier properties and stable adhesion to the base material layer 101, it is particularly preferably 0.15 μm to 0.45 μm or less.

Then, regarding (2) the coating layer is heated by a heating mechanism, and the carboxyl group contained in the polycarboxylic acid and the amine group contained in the polyamine compound undergo a dehydration condensation reaction, thereby forming The procedure of the gas barrier polymer layer 103 of the amide bond will be described.

In the method for manufacturing the gas-barrier laminate 100 of this embodiment, in order to obtain the gas-barrier polymer layer 103 of this embodiment, a method selected from the "conduction heat transfer method" that utilizes contact with a high-temperature body and uses At least one of the “radiation heat transfer methods” of 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 refers to a method of heating a material in contact with a high-temperature body by heat conduction. As a device for heating by a conduction heat transfer method, for example, a heating roller or the like can be mentioned. In the case of heating using a heating roller, heating is performed by bringing the heating roller into contact with the material. From the viewpoint of excellent heat conduction efficiency of the film, a heating roller is preferable.

The so-called radiant heat transfer method is a method that uses the radiation energy of infrared rays emitted by a high-temperature body as a heat source, and the infrared rays absorbed by the material become heat in the material to heat the material. As an infrared source, an infrared heater or an infrared lamp can be used.

In the step of forming the gas barrier polymer layer 103, the heat treatment temperature is preferably 160°C to 250°C, the heat treatment time is 1 second to 10 minutes, and the heat treatment temperature is preferably 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 base layer 101 side or from the coating layer side, and the gas barrier polymer layer 103 having excellent gas barrier properties may be obtained more stably From the viewpoint of heating, heating from the base material layer 101 side is preferred.

In addition, when heating the coating layer, a convection heat transfer type heating mechanism may be suitably used in combination. Here, the heating by convection heat transfer method is a heating method that uses heated air as hot air and makes it directly contact with the material, and can be caused by the relative speed of the material and the hot air, and the temperature difference between the material and the hot air The heat transfer caused is controlled.

As a device for heating by a convection heat transfer method, for example, a hot air dryer, a hot air oven, a dryer, etc. may be mentioned.

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

In the step of forming the gas barrier polymer layer 103, the coating layer may be dried before the heating of the coating layer. In addition, the drying and heat treatment may be performed simultaneously.

In the step of forming the gas barrier polymer layer 103, in the case where the coating layer is dried before the heat treatment, the drying temperature is preferably 60°C to 150°C and the drying time is 1 second to 60 seconds Under the drying.

The gas barrier polymer layer 103 of the present embodiment can be formed by the above-mentioned gas barrier coating material, and after applying the gas barrier coating material on the base material layer 101 or the inorganic material layer 102 described later, drying and heat treatment , Obtained by hardening the coating material for gas barrier.

Further, in the step of forming a gas barrier polymer layer 103, is heated until the infrared absorption spectrum of the resulting gas barrier polymer layer 103, the absorption band above 1493cm ^-1, 1780cm ^-1 or less of the total range of when the viewpoint of the peak area is a, the absorption band 1598cm ^-1 or more, and the total peak area in the range 1690cm ^-1 or less as B, the area ratio of Amides bond to B / a expressed from the gas barrier property than It 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 laminate 100 having further excellent gas-barrier performance can be obtained. Moreover, 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 below 0.650.

A gas barrier polymer layer 103 in the present embodiment, the infrared absorption spectrum based on unreacted carboxylic see the νC = O absorption near 1700cm ^-1, as seen on near 1630cm ^-1 ~ 1685cm ^-1 νC Amides bond crosslinked structure = O absorption near 1540cm ^-1 ~ 1560cm ^-1 see O absorption based νC = carboxylates.

That is, in the present embodiment, the infrared absorption spectrum of the absorption band above 1493cm ^-1, 1780cm ^-1 The following range of total peak area A represents the total amount of carboxylic acid with acyl amine carboxylates bond index, absorption ^-1 with 1598 or more, the range 1690cm ^-1 total peak area represented by B is present in an amount of Amides key index, the absorption band later than 1690cm ^-1, 1780 cm ^-1 range of the total peak area represented by unreacted C carboxylic acid is present in an amount of indicator, to be described later 1493cm ^-1 absorption band over the total peak area D range 1598cm ^-1 the following represents a carboxylate, i.e., a carboxyl group and amine group present in an amount of ionic crosslinking index.

In this embodiment, the total peak area A to the total peak area D can be measured in the following order.

First, a 1 cm×3 cm measurement sample was cut out from the gas barrier polymer layer 103 of this embodiment. Next, the infrared absorption spectrum of the surface of the gas barrier polymer layer 103 was obtained by infrared total reflection measurement (ATR (Attenuated Total Reflection) method). From the obtained infrared absorption spectrum, the total peak area A to the total peak area D were calculated by the following procedures (1) to (4).

(1) with a line (N) connecting 1780cm ^-1 1493cm ^-1 and the absorbance of the absorption band 1493cm ^-1 or more, and the absorption spectrum range of 1780cm ^-1 and less as the area N surrounded by total peak area A.

(2) The straight line (O) is drawn vertically from the absorbance (Q) of 1690cm ^-1 , the intersection of N and O is set to P, and the straight line (S) is drawn vertically from the absorbance (R) of 1598cm ^-1 , and N point of intersection S is T, the above absorption band 1598cm ^-1, 1690cm ^-1 range absorption spectrum of the straight line S, point T, the straight line N, the point P, the straight line O, absorbance Q, R surrounded by absorbance The area is taken as the total peak area B.

(3) The above absorption band 1690cm ^-1, 1780cm ^-1 of the absorption spectrum and absorbance less Q, straight line O, the point P, the straight line N as the area surrounded by the total peak area C.

(4) The total peak area D is the area surrounded by the absorption spectrum in the range of 1493 cm ^-1 or more and 1598 cm ^-1 or less, and the absorbance R, the straight line S, the point T, and the straight line N.

Next, the area ratios B/A, C/A, and D/A are obtained from the areas obtained by the above method.

In addition, for the measurement of the infrared absorption spectrum (infrared total reflection measurement: ATR method) of this embodiment, for example, an IRT-5200 device manufactured by Nippon Spectroscopy Co., Ltd. can be used, and a PKM-GE-S (germanium (Germanium)) crystal is mounted at an incident angle It was carried out under the conditions of 45 degrees, room temperature, resolution of 4 cm ^-1 , and cumulative count of 100 times.

The gas-barrier polymer layer 103 formed of a mixture containing a polycarboxylic acid and a polyamine compound has two kinds of cross-linked structures, ionic cross-linking and amide cross-linking. The existence ratio of these cross-linked structures is such that the gas barrier performance It is important in the improved viewpoint. In addition, the ionic cross-linking refers to the generation of acid-base reaction between the carboxyl group contained in the polycarboxylic acid and the amine group contained in the polyamine compound, and the amide crosslinking refers to the formation of the polycarboxylic acid The carboxyl group contained in it and the amine group contained in the polyamine compound produce a dehydration condensation reaction.

Therefore, it is used to make these two strips under high humidity and after boiling and cooking treatment. The design guidelines of improving the gas barrier properties such as oxygen barrier properties and water vapor barrier properties, and improving the performance balance of appearance, dimensional stability, and productivity can be applied to the area of the amide bond represented by the B/A The scale of the ratio. By controlling the manufacturing conditions, it becomes possible to adjust the area ratio of the amide bond represented by the B/A of the gas barrier polymer layer 103 to a specific value or more, and the gas barrier polymer layer 103 having such characteristics It more effectively shows the gas barrier properties under high humidity and after boiling and cooking treatments. In addition, the balance of appearance, dimensional stability and productivity is also excellent.

That is, by setting the area ratio of the amide bond represented by B/A to be above the lower limit, the oxygen barrier property and water under two conditions of high humidity and after boiling and cooking treatment can be obtained The gas barrier layered body 100 is further excellent in vapor barrier properties, and is excellent in balance of appearance, dimensional stability, and productivity.

The reason why such a gas barrier polymer layer 103 is excellent in the above-mentioned performance balance is not necessarily clear, and it is considered that the reason is that the area ratio of the amide bond represented by B/A is the gas barrier polymer layer within the above range The ionic cross-linking and amide cross-linking of these two cross-linking structures balance well to form a dense structure.

That is, the area ratio of the amide bond represented by the B/A within the range means that the two cross-linked structures of ionic crosslinking and amide crosslinking can be formed in a well-balanced manner.

Further, in the step of forming a gas barrier polymer layer 103, is heated until the infrared absorption spectrum of the resulting gas barrier polymer layer 103, the absorption band above 1690cm ^-1, 1780cm ^-1 or less of the total range of When the peak area is C, from the viewpoint of further improving the balance of appearance, dimensional stability, and productivity, the area ratio of the carboxylic acid represented by C/A is preferably 0.040 or more, and more preferably 0.060 or more. Preferably it is above 0.080.

Moreover, from the viewpoint of further improving the oxygen barrier properties and water vapor barrier properties under high humidity and under both conditions of boiling and cooking, the upper limit of the area ratio of the carboxylic acid represented by the C/A It is preferably 0.500 or less, more preferably 0.450 or less, and particularly preferably 0.400 or less.

Furthermore, in the step of forming the gas barrier polymer layer 103, heating is performed until the total absorption band 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 peak area is set to D, the carboxylate represented by D/A is considered from the viewpoint of further improving the oxygen barrier properties and water vapor barrier properties under high humidity and after boiling and retorting. The area ratio is preferably 0.100 or more, and more preferably 0.150 or more.

Moreover, from the viewpoint of further improving the balance of appearance, dimensional stability, and productivity, 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, and particularly preferably It is below 0.400.

In the gas barrier polymer layer 103 of the present embodiment, the area ratio of the amide bond represented by B/A, 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 this embodiment, in particular, the blending ratio of the polycarboxylic acid and the polyamine compound, the preparation method of the gas barrier coating material, the method of heat treatment of the gas barrier coating material, temperature, time, etc. are used to control the The area ratio of the amide bond represented by B/A, the area ratio of the carboxylic acid represented by C/A, and the The factors of the area ratio of the carboxylate represented by D/A are listed.

(Substrate layer)

The base material layer 101 of the present embodiment can be formed of, for example, an organic material such as thermosetting resin, thermoplastic resin, or paper, and preferably contains at least one selected from thermosetting resin and thermoplastic resin.

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

Examples of the thermoplastic resin include known thermoplastic resins such as polyolefin (polyethylene, polypropylene, poly(4-methyl-1-pentene), poly(1-butene), etc.) and polyester (polyterephthalic acid Ethylene glycol, polybutylene terephthalate, polyethylene naphthalate, etc.), polyamide (nylon-6, nylon-66, polyhexamethylene xylylenediamine, etc.), polyvinyl chloride , Polyimide, ethylene-vinyl acetate copolymer or its saponified product, polyvinyl alcohol, polyacrylonitrile, polycarbonate, polystyrene, ionic polymer, fluororesin, or a mixture of these.

Among these, from the viewpoint of improving transparency, it is preferably selected from polypropylene, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, and polyamide , Polyimide one or two or more, more preferably one or more selected from 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 application of the gas barrier laminate 100.

Furthermore, the thermosetting resin and the thermoplastic resin The film is extended in at least one direction, preferably in a biaxial direction, to form a substrate layer.

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

Furthermore, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, acrylic resin, urethane-based resin, etc. may be coated on the surface of the base material layer 101.

In addition, the base material layer 101 may be surface-treated in order to improve the adhesion to the gas barrier polymer layer 103. Specifically, surface activation treatment such as corona treatment, flame treatment, plasma treatment, under coat treatment, primer coat treatment, etc. may be performed.

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

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

(Inorganic layer)

As shown in FIG. 2, in the gas barrier laminate 100, the inorganic layer 102 may be further laminated between the base material layer 101 and the gas barrier polymer layer 103. As a result, the barrier properties such as oxygen barrier properties or water vapor barrier properties can be further improved.

Examples of the inorganic substance that constitutes the inorganic substance layer 102 of the present embodiment include metals, metal oxides, metal nitrides, metal fluorides, and metal oxynitrides that can form barrier films.

Examples of the inorganic substance constituting the inorganic substance layer 102 include elements from Group 2A of the periodic table such as beryllium, magnesium, calcium, strontium, and barium; transition elements from the Periodic Table of titanium, zirconium, ruthenium, hafnium, and tantalum; and Group 2B elements of the periodic table such as zinc; Element 3A of the periodic table such as aluminum, gallium, indium, thallium; element 4A of the periodic table such as silicon, germanium, tin; element 6A of the periodic table such as selenium, tellurium, oxide, nitride, fluoride, or nitrogen One or two or more oxides.

In addition, in this embodiment, the family name of the periodic table is represented by the old CAS formula.

In addition, among the inorganic substances, in consideration of excellent balance of self-blocking properties, cost, and the like, one or more inorganic substances selected from the group consisting of silica, alumina, and aluminum are preferred.

In addition, in addition to silicon dioxide, silicon oxide may also contain silicon monoxide and silicon monoxide.

The inorganic material layer 102 is composed of the inorganic material. The inorganic material layer 102 may be composed of a single inorganic material layer or a plurality of inorganic material layers. Moreover, when the inorganic material layer 102 is composed of a plurality of inorganic material layers, it may be composed of the same kind of inorganic material layer, or may be composed of different kinds 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 the balance of barrier properties, adhesiveness, handleability, and the like.

In this embodiment, the thickness of the inorganic layer 102 can be Obtained from the observation image of the sub-microscope or scanning electron microscope.

The method for forming the inorganic layer 102 is not particularly limited, and for example, vacuum deposition, ion plating, sputtering, chemical vapor deposition, physical vapor deposition, and chemical vapor deposition (CVD ( Chemical Vapor Deposition method), plasma CVD method, sol-gel method, etc. to form the inorganic substance layer 102 on one side or both sides of the base material layer 101. Among them, it is desirable to form a film under reduced pressure by sputtering, ion plating, chemical vapor deposition (CVD), physical vapor deposition (PVD (Physical Vapor Deposition)), plasma CVD, etc. . This allows chemically active molecular species containing silicon, such as silicon nitride or silicon oxynitride, to react quickly, thereby improving the smoothness of the surface of the inorganic layer 102 and reducing the number of holes.

When performing these binding reactions rapidly, it is desirable that the inorganic atom or compound is a chemically active molecular species or atomic species.

The gas-barrier laminate 100 of the present embodiment has excellent gas-barrier performance, and can be used as packaging materials, particularly food packaging materials that require high gas-barrier contents, medical applications, industrial applications, daily sundries applications, etc. Suitable for packaging materials.

Furthermore, the gas-barrier laminate 100 of the present embodiment can be suitably used as, for example, a film for vacuum heat insulation requiring high barrier performance; a film for sealing electroluminescent elements, solar cells, and the like.

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

[Example]

Hereinafter, this embodiment will be described in detail with reference to Examples and Comparative Examples. In addition, this embodiment is not limited at all by the description of these examples.

<Preparation of solution (Z)>

Add purified water to a mixture of ammonium polyacrylate (manufactured by East Asia Synthetic Co., Ltd., product name: ARON A-30, 30% by mass aqueous solution, molecular weight: 100,000) to obtain polyacrylic acid made into a 10% by mass solution Ammonia solution.

<Preparation of solution (Y)>

Purified water was added to polyethyleneimine (manufactured by Wako Pure Chemical Industries, Ltd., product name: polyethyleneimine, average molecular weight: about 10,000) to obtain a polyethyleneimine aqueous solution prepared as a 10% by mass solution.

[Example 1-1]

79 g of the ammonium polyacrylate aqueous solution (Z) and 21 g of the polyethyleneimine aqueous solution (Y) were mixed and stirred to prepare a mixed liquid.

Further, the purified water was added so that the solid content concentration of the mixed liquid became 2.5% by mass, and stirred until it became a uniform solution, and then the nonionic interface activity was mixed so that the solid content of the mixed liquid became 0.3% by mass. Agent (polyoxyethyl lauryl ether, manufactured by Kao Corporation, trade name: EMULGEN 120) to prepare a solution (V).

The obtained solution (V) was applied to a biaxial extension with a thickness of 12 μm by means of a mayer bar so that the thickness after heat treatment (that is, the film thickness of the gas barrier polymer layer) became 0.3 μm The corona treated surface of polyethylene terephthalate film (made by Unitika, PET12) uses a hot air dryer at Drying was performed under the conditions of a temperature of 100° C. and a time of 30 seconds, and a heat roller was further subjected to heat treatment at a temperature of 200° C. and a time of 60 seconds to obtain a gas-barrier laminated film.

[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 a dryer using a far infrared heater and hot air in combination.

[Comparative Example 1]

A gas-barrier laminated film was obtained in the same manner as in Example 1-1, except that the hot roller 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 temperature was 210° C. and the time was 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 a dryer using a far infrared heater and hot air in combination.

[Comparative Example 2]

A gas-barrier laminated film was obtained in the same manner as in Example 2-1, except that the hot roller was 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 temperature was 220° C. and the time was 45 seconds.

[Comparative Example 3]

A gas-barrier laminated film was obtained in the same manner as in Example 3 except that the hot roller was used as a hot air dryer.

The gas barrier multilayer films obtained in Examples and Comparative Examples were evaluated as follows. Table 1 shows the obtained results.

<Preparation of multilayer film for physical property evaluation>

(1) On one side of an unstretched polypropylene film (manufactured by Mitsui Chemicals Tohcello Co., Ltd., trade name: RXC-22) with a thickness of 70 μm, an ester adhesive (polyurethane) is applied Adhesive (made by Mitsui Chemicals, trade name: Takelac A525S): 9 parts by mass, isocyanate hardener (made by Mitsui Chemicals, trade name: Takenate A50): 1 Parts by mass and ethyl acetate: 7.5 parts by mass). After drying, it was bonded (dry lamination) to the gas barrier polymer layer of the gas barrier laminate film obtained in Examples and Comparative Examples to obtain a multilayer film.

(2) Steaming treatment

After folding the multilayer film obtained in the above (1) so that the unstretched polypropylene film becomes the inner surface, heat-sealing the both sides to form a bag shape, put 70cc of water as the content, by putting another The side was heat-sealed to make a bag, which was subjected to cooking treatment at 130° C. for 30 minutes in a high-temperature high-pressure cooking and sterilization device. After the cooking treatment, the water of the contents is removed to obtain a multilayer film after the cooking treatment.

(3) Oxygen permeability [ml/(m ² .day.MPa)]

Using OX-TRAN2/21 manufactured by Mocon, according to JIS K 7126, under the conditions of a temperature of 20°C and a humidity of 90% RH. The obtained multilayer film was measured.

(4) IR area ratio

The measurement of infrared absorption spectrum (infrared total reflection measurement: ATR method) is to use the IRT-5200 device manufactured by Japan Spectroscopy Co., Ltd., and install PKM-GE-S (germanium (Germanium)) crystal at an incident angle of 45 degrees, room temperature, The measurement was carried out under the conditions of a resolution of 4 cm ^-1 and a cumulative number of 100 times. The obtained absorption spectrum was analyzed by the method described above 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]

If Example 1-1, Example 1-2, and Comparative Example 1 having the same heat treatment time and temperature are compared, the amides of Example 1-1 and Example 1-2 heated using a hot roller or far infrared rays The ratio of bonds (B/A) is more than that of Comparative Example 1 using only a hot air dryer as the heating mechanism of the coating layer. That is, it is known that Examples 1-1 and 1-2 can produce the gas barrier polymer layer 103 having an amide cross-linked structure more efficiently than Comparative Example 1. In addition, it is known that such a gas barrier laminated film has a low oxygen permeability and more excellent gas barrier performance.

Furthermore, according to the comparative examples of Example 2-1, Example 2-2, and Comparative Example 2 having the same heat treatment time and temperature, or the comparative examples of Example 3 and Comparative Example 3, it is known that heating using a hot roller or far infrared rays The ratio of the amide bond (B/A) of the example of the example is more than the comparative example using only the hot air dryer as the heating mechanism of the coating layer.

Based on the above, the production method of the present invention can efficiently produce a gas barrier laminate having excellent gas barrier performance.

This application claims priority based on Japanese Patent Application No. 2015-103500 filed on May 21, 2015, and all the contents disclosed in this patent application are incorporated into this application.

100‧‧‧Gas-barrier laminate

101‧‧‧ Base layer

103‧‧‧Gas barrier polymer layer

Claims (7)

A method for manufacturing a gas-barrier laminate, which is a method for manufacturing a gas-barrier laminate including a substrate layer and a gas-barrier polymer layer provided on at least one surface of the substrate layer, and includes : A step of applying a coating material for gas barrier containing a polycarboxylic acid and a polyamine compound on a substrate layer to obtain a coating layer; drying the coating layer to coat the coating material for gas barrier A drying step for removing the solvent; and heating the dried coating layer with a heating mechanism so that the carboxyl group contained in the polycarboxylic acid and the amine group contained in the polyamine compound undergo a dehydration condensation reaction, Thereby, a heat treatment step of forming a gas barrier polymer layer having an amide bond, and the heating mechanism contains at least one selected from a conductive heat transfer method and a radiant heat transfer method, (the The number of moles of -COO- groups contained in the polycarboxylic acid)/(the number of moles of amine groups contained in the polyamine compound in the gas barrier coating material)=100/(over 22 ), 100/ (below 99). The method for manufacturing a gas-barrier laminate according to item 1 of the patent application range, wherein the heating mechanism includes at least one selected from conductive heat transfer using a heating roller and radiant heat transfer using infrared rays. The method for manufacturing a gas-barrier laminate according to the first or second patent application scope, wherein the heating mechanism further includes a convection heat transfer method. The method for manufacturing a gas-barrier laminate as described in item 1 or 2 of the patent application range, wherein in the step of forming the gas-barrier polymer layer, heating is performed until the resulting gas-barrier polymerization layer infrared absorption spectrum, the absorption band 1493cm ^-1 or more, and the total peak area in the range 1780cm ^-1 or less is a, the absorption band 1598cm ^-1 or more, and the total peak area in the range 1690cm ^-1 to less In the case of B, the area ratio of the amide bond represented by B/A is 0.330 or more. The method for manufacturing a gas-barrier laminate according to the first or second patent application, wherein the drying temperature of the drying step is 60°C to 150°C, and the heat treatment temperature of the heat treatment step is 160°C ~250℃. The method for manufacturing a gas-barrier laminate according to the first or second patent application scope, wherein the polycarboxylic acid comprises a polyacrylic acid, polymethacrylic acid, copolymer of acrylic acid and methacrylic acid One or more than two polymers. The method for producing a gas-barrier laminate according to the first or second patent application, wherein the polyamine compound contains polyethyleneimine.

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