JPWO2016186075A1 - Method for producing gas barrier laminate - Google Patents

Abstract

The method for producing a gas barrier laminate (100) of the present invention comprises a base material layer (101) and a gas barrier polymer layer (103) provided on at least one surface of the base material layer (101). A method for producing a gas barrier laminate (100), in which a mixture containing a polycarboxylic acid and a polyamine compound is applied to a substrate layer (101) to obtain a coating layer, and the coating layer is formed by heating means. And heating to form a gas barrier polymer layer (103) having an amide bond by subjecting a carboxyl group contained in the polycarboxylic acid and an amino group contained in the polyamine compound to a dehydration condensation reaction. . And the said heating means contains at least 1 type selected from a conduction heat transfer system and a radiation heat transfer system.

Description

  The present invention relates to a method for producing a gas barrier laminate.

In general, as a gas barrier material, a laminate in which an inorganic layer which is a gas barrier layer is provided on a base material layer is used.
However, this inorganic layer is weak against friction and the like, and such a gas barrier laminate has a gas barrier property due to cracks and elongation caused by rubbing and elongation at the time of post-processing printing, lamination or filling of contents. May decrease.
Therefore, as a gas barrier material, a laminate using an organic layer as a gas barrier layer is also used.

As a gas barrier material using an organic material 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 the technology related to such a gas barrier laminate include those described in Patent Document 1 (Japanese Patent Laid-Open No. 2005-225940) and Patent Document 2 (Japanese Patent Laid-Open No. 2013-10857).

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

In Patent Document 2, polyamine / polycarboxylic acid = 12.5 / 87.5 to 27.5 / 72.5 in a weight ratio of polyamine and polycarboxylic acid on at least one surface of a base material made of a plastic film. A film coated with a mixture obtained by mixing with is disclosed.
Patent Document 2 describes that such a gas barrier film is excellent in gas barrier properties, particularly oxygen barrier properties, and excellent in flexibility, transparency, moisture resistance, chemical resistance, etc. even after the boil treatment.

JP 2005-225940 A JP 2013-10857 A

  According to the study by the present inventors, the gas barrier film as described in Patent Documents 1 and 2 requires heating at a high temperature for a long time in order to crosslink the polycarboxylic acid and the polyamine. It became clear that there is still room for improvement in terms of productivity.

  The present invention has been made in view of the above circumstances, and provides a production method capable of efficiently producing a gas barrier laminate having an amide crosslinked structure formed by a polyamine compound and a polycarboxylic acid, which is excellent in gas barrier performance. To do.

  The inventors of the present invention have made extensive studies in order to achieve the above problems. As a result, by heating the mixture containing the polycarboxylic acid and the polyamine compound by a specific heating means, a dehydration condensation reaction between the carboxyl group contained in the polycarboxylic acid and the amino group contained in the polyamine compound occurs efficiently, The present invention was completed by obtaining the knowledge that a gas barrier laminate having an amide crosslinked structure formed of a polyamine compound and a polycarboxylic acid, which is excellent in gas barrier performance, can be efficiently produced.

  That is, according to this invention, the manufacturing method of the gas-barrier laminated body shown below is provided.

[1]
A gas barrier laminate manufacturing method comprising: a base material layer; and a gas barrier polymer layer provided on at least one surface of the base material layer,
Applying a mixture containing a polycarboxylic acid and a polyamine compound to a base material layer to obtain a coating layer;
The coating layer is heated by a heating means, and a gas barrier polymer layer having an amide bond is formed by dehydration condensation reaction between a carboxyl group contained in the polycarboxylic acid and an amino group contained in the polyamine compound. Process,
Including
The manufacturing method of the gas-barrier laminated body in which the said heating means contains at least 1 type selected from a conduction heat transfer system and a radiation heat transfer system.
[2]
The method for producing a gas barrier laminate according to the above [1], wherein the heating means includes at least one selected from conduction heat transfer by a heating roll and radiation heat transfer by infrared rays.
[3]
The method for producing a gas barrier laminate according to the above [1] or [2], wherein the heating means further comprises a convection heat transfer system.
[4]
In the step of forming the gas barrier polymer layer,
In the infrared absorption spectrum of the obtained gas barrier polymer layer,
The total peak area in the range of the absorption band 1493 cm ^{−1 to} 1780 cm ⁻¹ is A,
When the total peak area in the range of the absorption band 1598cm ^-1 or 1690 cm ^-1 and is B,
The method for producing a gas barrier laminate according to any one of [1] to [3], wherein heating is performed until the area ratio of the amide bond represented by B / A is 0.330 or more.
[5]
(The number of moles of —COO— groups contained in the polycarboxylic acid in the mixture) / (the number of moles of amino groups contained in the polyamine compound in the mixture) = over 100/22 and up to 100/99, The method for producing a gas barrier laminate according to any one of the above [1] to [4].
[6]
Any one of the above [1] to [5], wherein the polycarboxylic acid includes one or two or more polymers selected from polyacrylic acid, polymethacrylic acid, and a copolymer of acrylic acid and methacrylic acid. The manufacturing method of the gas-barrier laminated body as described in one.
[7]
The method for producing a gas barrier laminate according to any one of [1] to [6], wherein the polyamine compound includes polyethyleneimine.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method which can manufacture efficiently the gas barrier property laminated body which has the amide bridge | crosslinking structure formed of the polyamine compound and polycarboxylic acid which is excellent in gas barrier performance can be provided.

  The above-described object and other objects, features, and advantages will become more apparent from the preferred embodiments described below and the accompanying drawings.

It is sectional drawing which showed typically an example of the structure of the gas-barrier laminated body of embodiment which concerns on this invention. It is sectional drawing which showed typically an example of the structure of the gas-barrier laminated body of embodiment which concerns on this invention.

  Embodiments of the present invention will be described below with reference to the drawings. In addition, the figure is a schematic diagram and does not match the actual dimensional ratio. In addition, "-" between the numbers in a sentence represents the following from the above, unless there is particular notice.

<Method for producing gas barrier laminate>
1 and 2 are cross-sectional views schematically showing an example of the structure of a gas barrier laminate 100 according to an embodiment of the present invention.
The gas barrier laminate 100 is provided on the base layer 101 and at least one surface of the base layer 101, and heats a mixture containing a polycarboxylic acid and a polyamine compound (hereinafter also referred to as a gas barrier coating material). And a gas barrier polymer layer 103 formed by doing so.

Hereinafter, an example of the manufacturing method of the gas barrier laminate 100 according to the present embodiment will be described.
The manufacturing method of the gas barrier laminate 100 according to the present embodiment includes (1) a step of applying a mixture containing a polycarboxylic acid and a polyamine compound to the base material layer 101 to obtain a coating layer, and (2) a heating means. The step of forming the gas barrier polymer layer 103 having an amide bond by heating the coating layer by dehydration condensation reaction between the carboxyl group contained in the polycarboxylic acid and the amino group contained in the polyamine compound And including. In the step (2), the heating means includes at least one selected from a conduction heat transfer method and a radiation heat transfer method.

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

First, a gas barrier coating material is prepared.
The gas barrier coating material can be prepared, 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, the 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 such a procedure, the formation of aggregates of the polycarboxylic acid and the polyamine compound can be suppressed, and a uniform gas barrier coating material can be obtained. Thereby, the dehydration condensation reaction between the —COO— group contained in the polycarboxylic acid and the amino group contained in the polyamine compound can be promoted more effectively.

By neutralizing the polycarboxylic acid with the base according to the present embodiment, gelation can be suppressed when the polyamine compound and the polycarboxylic acid are mixed. Therefore, in the polycarboxylic acid, it is preferable to use a partially neutralized product or a completely neutralized product of the carboxyl group with a base from the viewpoint of preventing gelation. The neutralized product can be obtained by partially or completely neutralizing the carboxyl group of the polycarboxylic acid with a base (that is, partially or completely converting the carboxyl group of the polycarboxylic acid into a carboxylate). . Thereby, gelatinization can be prevented when adding a polyamine compound.
The partially neutralized product is prepared by adding a base to an aqueous solution of a polycarboxylic acid, but a desired degree of neutralization can be achieved by adjusting the amount ratio of the polycarboxylic acid and the base. In the present embodiment, the degree of neutralization of the base of the polycarboxylic acid is preferably 30 to 100 equivalent%, and preferably 40 to 100 from the viewpoint of sufficiently suppressing gelation due to the neutralization reaction with the amino group of the polyamine compound. Equivalent%, more preferably 50 to 100 equivalent%.

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

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

(Blend ratio of polycarboxylic acid and polyamine compound)
In the present embodiment, (the number of moles of —COO— groups contained in the polycarboxylic acid in the gas barrier coating material) / (the number of moles of amino groups contained in the polyamine compound in the gas barrier coating material) is preferably 100. / 22, more preferably 100/25 or more, particularly preferably 100/29 or more.
On the other hand, in the present embodiment, (the number of moles of —COO— groups contained in the polycarboxylic acid in the gas barrier coating material) / (the number of moles of amino groups contained in the polyamine compound in the gas barrier coating material) is preferably Is 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 according to the present embodiment, (the number of moles of —COO— group contained in the polycarboxylic acid in the gas barrier coating material) / (included in the polyamine compound in the gas barrier coating material) It is preferable to adjust the blending ratio of the polycarboxylic acid and the polyamine compound in the gas barrier coating material so that the number of moles of amino groups to be within the above range.

(Polycarboxylic acid)
The polycarboxylic acid according to this embodiment has two or more carboxyl groups in the molecule. Specifically, homopolymers of α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, cinnamic acid, 3-hexenoic acid, 3-hexenedioic acid, or the like A copolymer is mentioned. Further, it may be a copolymer of the α, β-unsaturated carboxylic acid and esters such as ethyl ester, olefins such as ethylene, and the like.
Among these, a homopolymer of acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, cinnamic acid or a copolymer thereof is preferable, and polyacrylic acid, polymethacrylic acid, a copolymer of acrylic acid and methacrylic acid is preferable. More preferably, it is one or two or more polymers selected from polymers, more preferably at least one polymer selected from polyacrylic acid and polymethacrylic acid, and a homopolymer of acrylic acid Particularly preferred is at least one polymer selected from homopolymers of methacrylic acid.
Here, in this embodiment, polyacrylic acid includes both a homopolymer of acrylic acid and a copolymer of acrylic acid and other monomers. In the case of a copolymer of acrylic acid and another monomer, polyacrylic acid has a structural unit derived from acrylic acid in 100% by mass of the polymer, usually 90% by mass or more, preferably 95% by mass or more. Preferably it contains 99 mass% or more.
In the present embodiment, polymethacrylic acid includes both a homopolymer of methacrylic acid and a copolymer of methacrylic acid and other monomers. In the case of a copolymer of methacrylic acid and another monomer, polymethacrylic acid has a structural unit derived from methacrylic acid, usually 90% by mass or more, preferably 95% by mass or more, in 100% by mass of the polymer. Preferably it contains 99 mass% or more.

The polycarboxylic acid according to this embodiment is a polymer obtained by polymerizing carboxylic acid monomers, and the molecular weight of the polycarboxylic acid is preferably 500 to 2,000,000 from the viewpoint of excellent balance between gas barrier properties and handleability. 500 to 1,000,000 is more preferable. Furthermore, 5,000-500,000 are preferable and 10,000-100,000 are especially preferable.
Here, in this embodiment, the molecular weight of the polycarboxylic acid is a weight average molecular weight in terms of polyethylene oxide, and can be measured using gel permeation chromatography (GPC).

(Polyamine compound)
The polyamine compound according to this embodiment is a polymer having two or more amino groups in the main chain, side chain, or terminal. Specific examples include aliphatic polyamines such as polyallylamine, polyvinylamine, polyethyleneimine, and poly (trimethyleneimine); polyamides having an amino group in the side chain such as polylysine and polyarginine; and the like. Moreover, the polyamine which modified some amino groups may be sufficient. From the viewpoint of obtaining good gas barrier properties, polyethyleneimine is more preferable.

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

  In addition, it is preferable to further add a surfactant to the gas barrier coating material from the viewpoint of preventing the occurrence of repelling during coating. The addition amount of the surfactant is preferably 0.01 to 3% by mass, and more preferably 0.01 to 1% by mass, when the total solid content of the gas barrier coating material is 100% by mass.

  Examples of the surfactant according to this embodiment include an anionic surfactant, a nonionic surfactant, a cationic surfactant, an amphoteric surfactant, and the like, from the viewpoint of obtaining good coatability. Therefore, nonionic surfactants are preferable, and polyoxyethylene alkyl ethers are more preferable.

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

Examples of the polyoxyalkylene alkylaryl ethers include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, and the like.
Examples of polyoxyalkylene alkyl ethers include polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether and polyoxyethylene lauryl ether.
Examples of polyoxyalkylene fatty acid esters include polyoxyethylene oleate, polyoxyethylene laurate, polyoxyethylene distearate, and the like.
Examples of sorbitan fatty acid esters include sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate and the like.
Examples of silicone surfactants include dimethylpolysiloxane.
Examples of the acetylene alcohol surfactant include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3, 5-dimethyl-1-hexyne-3ol and the like can be mentioned.
Examples of the fluorine-containing surfactant include a fluorine alkyl ester.

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

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

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

The thickness (wet thickness) of the coating layer is preferably 0.05 to 300 μm, more preferably 1 to 200 μm, still more preferably 1 to 100 μm, and particularly preferably 0.05 to 30 μm.
It can suppress that the gas barrier laminated body 100 obtained as the thickness of a coating layer is below the said upper limit, curls. Further, when the thickness of the coating layer is not more than the above upper limit value, the dehydration condensation reaction between the —COO— group contained in the polycarboxylic acid and the amino group contained in the polyamine compound can be promoted more effectively. .
Moreover, the barrier performance of the gas-barrier laminated body 100 obtained as the thickness of a coating layer is more than the said lower limit can be made more favorable.
The thickness of the gas barrier polymer layer 103 after the heat treatment is preferably 0.01 to 15 μm, more preferably 0.05 to 5 μm, still more preferably 0.1 to 1 μm, and the gas barrier property and the stability with the base material layer 101 are stable. In particular, 0.15 to 0.45 [mu] m or less is preferable because of excellent balance of adhesion.

  Subsequently, (2) gas barrier properties having an amide bond by heating the coating layer by a heating means and causing a dehydration condensation reaction between a carboxyl group contained in the polycarboxylic acid and an amino group contained in the polyamine compound. A process for forming the polymer layer 103 will be described.

In the method for producing the gas barrier laminate 100 of the present embodiment, in order to obtain the gas barrier polymer layer 103 according to the present embodiment, as a means for heating the coating layer, “conduction conduction” by contact with a high temperature body. At least one selected from “thermal system” and “radiant heat transfer system” by heat radiation from a high temperature body is adopted.
Thereby, the dehydration condensation reaction of the carboxyl group contained in the polycarboxylic acid and the amino group contained in the polyamine compound can be efficiently advanced.

The conduction heat transfer method is a method of heating a material in contact with a high-temperature body by heat conduction, and examples of a device that performs heating by the conduction heat transfer method include a heating roll. In the case of heating with a heating roll, heating is performed by bringing the heating roll into contact with the material. The heating roll is preferable from the viewpoint of being excellent in the efficiency of heat conduction to the film.
The radiant heat transfer method is a method in which infrared radiation energy emitted from a high-temperature body is used as a heat source. Infrared light absorbed by the material is changed into heat in the material to heat the material. As the infrared source, an infrared heater, an infrared lamp, or the like is used.

  In the step of forming the gas barrier polymer layer 103, the heat treatment temperature is 160 to 250 ° C, the heat treatment time is 1 second to 10 minutes, preferably the heat treatment temperature is 180 to 240 ° C, and the heat treatment time is 5 seconds to 5 seconds. More preferably, the heat treatment is performed under the conditions of a heat treatment temperature of 190 ° C. to 230 ° C. and a heat treatment time of 10 seconds to 2 minutes.

  When the coating layer is heated, it may be heated from the base material layer 101 side or from the coating layer side, but the gas barrier polymer layer 103 having excellent gas barrier performance can be made more stable. From the viewpoint of obtaining, it is preferable to heat from the base material layer 101 side.

Moreover, when heating the said coating layer, you may combine suitably the heating means by a convection heat transfer system. Here, heating by the convection heat transfer method is a heating method in which heated air is used as hot air and is brought into direct contact with the material. The heat transfer is caused by the relative speed between the material and hot air and the temperature difference between the material and hot air. It is controlled by the amount of heat.
Examples of the apparatus that performs heating by the convection heat transfer method include a hot air dryer, a hot air oven, and a dryer.

  From the viewpoint of effectively promoting the dehydration condensation reaction between the —COO— group contained in the polycarboxylic acid and the amino group contained in the polyamine compound, the heat treatment temperature and the heat treatment time depend on the wet thickness of the gas barrier coating material. It is important to make adjustments.

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, you may perform the said drying and heat processing simultaneously.
In the step of forming the gas barrier polymer layer 103, when drying is performed before the heat treatment of the coating layer, drying may be performed under conditions of a drying temperature: 60 to 150 ° C. and a drying time: 1 second to 60 seconds. desirable.

  The gas barrier polymer layer 103 according to the present embodiment is formed by the gas barrier coating material described above. After the gas barrier coating material is applied to the base material layer 101 or the inorganic layer 102 described later, the gas barrier polymer layer 103 is dried. It is obtained by performing a heat treatment to cure the gas barrier coating material.

In the step of forming the gas barrier polymer layer 103, in the infrared absorption spectrum of the obtained gas barrier polymer layer 103, the total peak area in the range from 1493 cm ^{−1 to} 1780 cm ⁻¹ is A, and the absorption band when the total peak area in the range of 1598cm ^-1 or 1690 cm ^-1 or less as B, B / is preferably the area ratio of the amide bond from the viewpoint of gas barrier properties represented by a 0.330 or more, more preferably 0.370 As mentioned above, it heats until it becomes 0.400 or more, Especially preferably, it becomes 0.420 or more. Thereby, the gas-barrier laminated body 100 which was further excellent in gas barrier performance can be obtained. 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, particularly from the viewpoint of further improving the balance of appearance, dimensional stability, and productivity. Preferably it is 0.650 or less.

In the gas barrier polymer layer 103 according to this embodiment, the absorption based on νC═O of the unreacted carboxylic acid in the infrared absorption spectrum is observed in the vicinity of 1700 cm ⁻¹ , and the absorption based on νC═O of the amide bond which is a crosslinked structure Is observed in the vicinity of 1630 to 1685 cm ⁻¹ , and absorption based on νC═O of the carboxylate is observed in the vicinity of 1540 to 1560 cm ⁻¹ .
That is, in this embodiment, the total peak area A in the range of the absorption band 1493 cm ⁻¹ or more and 1780 cm ⁻¹ or less in the infrared absorption spectrum represents an index of the total amount of carboxylic acid, amide bond, and carboxylate, and the absorption band 1598 cm. total peak area B in the range of ^-1 to 1690 cm ^-1 or less represents an indication of the presence of the amide bond, the total peak area C in the range of less absorption band 1690 cm ^-1 or more 1780 cm ^-1, which will be described later unreacted carboxylic acid represents an indication of the abundance, the total peak area D in the range of less absorption band 1493cm ^-1 or 1598cm ^-1 to be described later represents a carboxylate, i.e., an indication of the presence of ionic crosslinking of the carboxyl group and an amino group it is conceivable that.

In the present embodiment, the total peak areas A to D can be measured by the following procedure.
First, a measurement sample of 1 cm × 3 cm is 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 infrared total reflection measurement (ATR method). The total peak areas A to D are calculated from the obtained infrared absorption spectrum by the following procedures (1) to (4).
(1) 1780 cm connected by ^-1 and the linear absorbance 1493cm ^-1 (N), the area surrounded by the absorption spectra and N of the absorption band 1493Cm ^-1 or 1780 cm ^-1 or less in the range that the total peak area A.
(2) The straight line (O) is lowered vertically from the absorbance (Q) of 1690 cm ⁻¹ , the intersection of N and O is defined as P, and the straight line (S) is lowered vertically from the absorbance (R) of 1598 cm ^−1. the intersection S is T, the absorption spectrum and the straight line S of the absorption band 1598cm ^-1 or 1690 cm ^-1 or less in the range, the point T, the straight line N, the point P, the straight line O, absorbance Q, the total peak area surrounded by absorbance R It is assumed that area B.
(3) the absorption spectrum and absorbance Q absorption bands 1690 cm ^-1 or 1780 cm ^-1 or less in the range, the linear O, a point P, and the area surrounded by straight lines N and total peak area C.
(4) The area surrounded by the absorption spectrum in the range of 1493 cm ^{−1 to} 1598 cm ⁻¹ and the absorbance R, straight line S, point T, and straight line N is defined as the total peak area D.
Next, area ratios B / A, C / A, and D / A are obtained from the areas obtained by the above method.
In addition, the measurement of the infrared absorption spectrum of this embodiment (infrared total reflection measurement: ATR method) is performed by using, for example, an IRT-5200 apparatus manufactured by JASCO Corporation and mounting a PKM-GE-S (Germanium) crystal. The measurement can be performed under the conditions of 45 degrees, room temperature, resolution of 4 cm ⁻¹ , and integration count of 100 times.

The gas barrier polymer layer 103 formed of a mixture containing a polycarboxylic acid and a polyamine compound has two types of cross-linked structures, ionic cross-linking and amide cross-linking, and the presence ratio of these cross-linked structures improves the gas barrier performance. Is important. The ionic crosslinking is generated by causing an acid-base reaction between a carboxyl group contained in the polycarboxylic acid and an amino group contained in the polyamine compound, and the amide crosslinking is contained in the polycarboxylic acid. It is produced by causing a dehydration condensation reaction between the carboxyl group to be produced and the amino group contained in the polyamine compound.
Therefore, to improve the performance balance of appearance, dimensional stability, and productivity while improving gas barrier performance such as oxygen barrier properties and water vapor barrier properties under both high humidity and after boil / retort treatment As a design guideline, a scale of area ratio of amide bond represented by B / A can be applied. By controlling the production conditions, it becomes possible to adjust the area ratio of the amide bond represented by B / A of the gas barrier polymer layer 103 to a specific value or more, and the gas barrier polymer layer having such characteristics. No. 103 exhibits more effective gas barrier properties under both high humidity and after boil-retort treatment, and also has an excellent balance of appearance, dimensional stability, and productivity.
That is, by setting the area ratio of the amide bond represented by B / A to the above lower limit value or more, the oxygen barrier property and the water vapor barrier property under both high humidity and after the boil / retort treatment are further improved. However, the gas barrier laminate 100 having an excellent balance of appearance, dimensional stability, and productivity can be obtained.

The reason why such a gas barrier polymer layer 103 is excellent in the above performance balance is not necessarily clear, but the gas barrier polymer layer in which the area ratio of amide bonds represented by B / A is within the above range is described above. This is probably because the two types of cross-linking structures, ionic cross-linking and amide cross-linking, form a dense structure with a good balance.
That is, if the area ratio of the amide bond represented by B / A is within the above range, it is considered that the two types of cross-linked structures, ionic cross-linking and amide cross-linking, are formed in a well-balanced manner. .

Further, in the step of forming a gas barrier polymer layer 103, in the infrared absorption spectrum of the gas barrier polymer layer 103 obtained when the total peak area in the range of the absorption band 1690 cm ^-1 or 1780 cm ^-1 and as 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, more preferably 0.060 or more, and particularly preferably 0.8. Heat until 080 or higher.
In addition, the upper limit of the area ratio of the carboxylic acid represented by C / A is from the viewpoint of further improving the oxygen barrier property and the water vapor barrier property under both high humidity and after boil-retort treatment. Preferably it is 0.500 or less, More preferably, it is 0.450 or less, Most preferably, it is 0.400 or less.

Further, in the step of forming the gas barrier polymer layer 103, in the infrared absorption spectrum of the obtained gas barrier polymer layer 103, when the total peak area in the range of the absorption band 1493 cm ^{−1 to} 1598 cm ⁻¹ is D, The area ratio of the carboxylate salt represented by D / A is preferably from the viewpoint of further improving oxygen barrier properties and water vapor barrier properties under both high humidity and after boil-retort treatment. Heating is performed to 100 or more, more preferably 0.150 or more.
Moreover, the upper limit of the area ratio of the carboxylate represented by 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. Especially preferably, it is 0.400 or less.

  The area ratio of the amide bond indicated by B / A, the area ratio of carboxylic acid indicated by C / A, and the area ratio of carboxylate indicated by D / A of the gas barrier polymer layer 103 according to the present embodiment are as follows: It can be controlled by appropriately adjusting the manufacturing conditions of the gas barrier polymer layer 103. In the present embodiment, the mixing ratio of the polycarboxylic acid and the polyamine compound, the method for preparing the gas barrier coating material, the heat treatment method, the temperature, the time, etc. of the gas barrier coating material are the amides represented by B / A. It is mentioned as a factor for controlling the area ratio of the bond, the area ratio of the carboxylic acid represented by C / A and the area ratio of the carboxylate represented by D / A.

(Base material layer)
The base material layer 101 of the present embodiment is formed of, for example, an organic material such as a thermosetting resin, a thermoplastic resin, or paper, and includes at least one selected from a thermosetting resin and a thermoplastic resin. Is preferred.

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

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

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

  As the base material layer 101 of this embodiment, from the viewpoint of excellent transparency, rigidity, and heat resistance, one or two or more kinds of heat selected from polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyamide, and polyimide are used. A biaxially stretched film formed of a plastic resin is preferable, and a biaxially stretched film formed of one or more thermoplastic resins selected from polyethylene terephthalate and polyethylene naphthalate is more preferable.

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

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

  Although the shape of the base material layer 101 is not specifically limited, For example, shapes, such as a sheet | seat or film shape, a tray, a cup, a hollow body, are mentioned.

(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. Thereby, barrier performance, such as oxygen barrier property and water vapor | steam barrier property, can further be improved.

Examples of the inorganic material constituting the inorganic material layer 102 of the present embodiment include metals, metal oxides, metal nitrides, metal fluorides, and metal oxynitrides that can form a thin film having a barrier property.
Examples of the inorganic substance constituting the inorganic layer 102 include periodic table 2A elements such as beryllium, magnesium, calcium, strontium, and barium; periodic table transition elements such as titanium, zirconium, ruthenium, hafnium, and tantalum; and a periodic table such as zinc. Group 2B element; periodic table 3A element such as aluminum, gallium, indium, thallium; periodic table 4A element such as silicon, germanium, tin; simple substance such as 6A group element of periodic table such as selenium, tellurium, oxide, nitriding 1 type, or 2 or more types selected from the thing, fluoride, oxynitride, etc. can be mentioned.
In the present embodiment, the family name of the periodic table is shown by the old CAS formula.

Furthermore, among the inorganic materials, one or two or more inorganic materials selected from the group consisting of silicon oxide, aluminum oxide, and aluminum are preferable because of excellent balance between barrier properties and cost.
In addition to silicon dioxide, silicon oxide may contain silicon monoxide and silicon suboxide.

  The inorganic layer 102 is composed of the inorganic material. The inorganic layer 102 may be composed of a single inorganic layer or a plurality of inorganic layers. Further, when the inorganic layer 102 is composed of a plurality of inorganic layers, it may be composed of the same kind of inorganic layer, or may be composed of different kinds of inorganic layers.

The thickness of the inorganic layer 102 is usually 1 nm or more and 1000 nm or less, preferably 1 nm or more and 500 nm or less, from the viewpoint of the balance of barrier properties, adhesion, handling properties and the like.
In the present embodiment, the thickness of the inorganic layer 102 can be obtained from an observation image obtained by a transmission electron microscope or a scanning electron microscope.

The formation method of the inorganic layer 102 is not particularly limited, and for example, a vacuum deposition method, an ion plating method, a sputtering method, a chemical vapor deposition method, a physical vapor deposition method, a chemical vapor deposition method (CVD method), plasma CVD. The inorganic layer 102 can be formed on one surface or both surfaces of the base material layer 101 by a method, a sol-gel method, or the like. Of these, film formation under reduced pressure such as sputtering, ion plating, chemical vapor deposition (CVD), physical vapor deposition (PVD), and plasma CVD is desirable. As a result, the chemically active molecular species containing silicon, such as silicon nitride and silicon oxynitride, react quickly to improve the surface smoothness of the inorganic layer 102 and reduce the number of holes. It is expected to be.
In order to perform these bonding reactions quickly, 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 is excellent in gas barrier performance and includes various materials such as packaging materials, food packaging materials of contents requiring particularly high gas barrier properties, medical uses, industrial uses, daily miscellaneous goods, and the like. It can also be suitably used as a packaging material.
Further, the gas barrier laminate 100 of the present embodiment is suitable as, for example, a vacuum heat insulating film that requires high barrier performance; a sealing film for sealing electroluminescent elements, solar cells, and the like. Can be used for

  As mentioned above, although embodiment of this invention was described with reference to drawings, these are the illustrations of this invention, Various structures other than the above are also employable.

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

<Preparation of solution (Z)>
Ammonium polyacrylate aqueous solution prepared by adding purified water to a mixture of ammonium polyacrylate (product of Toa Gosei Co., Ltd., product name: Aron A-30, 30% by mass aqueous solution, molecular weight: 100,000) to make a 10% by mass solution. Got.
<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 in a 10% by mass solution.

[Example 1-1]
79 g of the ammonium polyacrylate aqueous solution (Z) and 21 g of the polyethylene imine aqueous solution (Y) were mixed and stirred to prepare a mixed solution.
Furthermore, after adding purified water so that the solid content concentration of the mixed solution is 2.5% by mass and stirring until a uniform solution is obtained, a nonionic surfactant (polyoxyethylene lauryl ether, manufactured by Kao Corporation) is added. , Trade name: Emulgen 120) was mixed at 0.3% by mass with respect to the solid content of the mixed solution to prepare a solution (V).
The obtained solution (V) was subjected to heat treatment with a Mayer bar on the corona-treated surface of a 12 μm-thick biaxially stretched polyethylene terephthalate film (Unitika, PET12) (that is, the film thickness of the gas barrier polymer layer). ) Is 0.3 μm, dried using a hot air dryer at a temperature of 100 ° C. for a time of 30 seconds, and further heated by a hot roll at a temperature of 200 ° C. for a time of 60 seconds. Was subjected to heat treatment to obtain a gas barrier laminate film.

[Example 1-2]
A gas barrier laminate film was obtained in the same manner as in Example 1-1 except that the hot roll was a dryer using both a far infrared heater and hot air.

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

[Example 2-1]
A gas barrier laminate film was obtained in the same manner as in Example 1-1 except that the heat treatment was performed under the conditions of temperature; 210 ° C., time; 60 seconds.

[Example 2-2]
A gas barrier laminate film was obtained in the same manner as in Example 2-1, except that the heat roll was a dryer using a combination of a far infrared heater and hot air.

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

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

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

  The following evaluation was performed about the gas-barrier laminated | multilayer film obtained by the Example and the comparative example. The obtained results are shown in Table 1.

<Production of multilayer film for physical property evaluation>
(1) On one side of an unstretched polypropylene film (trade name: RXC-22, manufactured by Mitsui Chemicals, Inc.) having a thickness of 70 μm, an ester adhesive (polyurethane adhesive (trade name: Takelac A525S, manufactured by Mitsui Chemicals): 9 Part by mass, an isocyanate curing agent (trade name: Takenate A50, manufactured by Mitsui Chemicals Co., Ltd .: 1 part by mass and ethyl acetate: 7.5 parts by mass) were applied. After drying, the gas barrier polymer layer surfaces of the gas barrier laminated films obtained in Examples and Comparative Examples were bonded together (dry lamination) to obtain a multilayer film.

(2) Retort treatment The multi-layer film obtained in (1) above is folded so that the unstretched polypropylene film becomes the inner surface, heat-sealed on both sides and formed into a bag shape, and then 70 cc of water is added as the contents. One side was heat-sealed to make a bag, and this was retort-treated at 130 ° C. for 30 minutes with a high-temperature and high-pressure retort sterilizer. After the retort treatment, the contents were drained to obtain a multilayer film after the retort treatment.

(3) Oxygen permeability [ml / (m ² · day · MPa)]
The multilayer film obtained by the above method was measured under the conditions of a temperature of 20 ° C. and a humidity of 90% RH according to JIS K 7126 using OX-TRAN2 / 21 manufactured by Mocon.

(4) IR area ratio Infrared absorption spectrum measurement (infrared total reflection measurement: ATR method) uses an IRT-5200 apparatus manufactured by JASCO Corporation, and a PKM-GE-S (Germanium) crystal is attached and an incident angle is 45 degrees. The measurement was performed under the conditions of room temperature, resolution of 4 cm ⁻¹ , and integration count of 100 times. The obtained absorption spectrum was analyzed by the method described above, and the total peak areas A to D were calculated. And area ratio B / A, C / A, D / A was calculated | required from all the peak areas AD.

When Examples 1-1, 1-2 and Comparative Example 1 having the same heat treatment time and temperature are compared, a hot roll or a farther than Comparative Example 1 using only a hot air dryer as the heating means of the coating layer is compared. The ratio of the amide bond (B / A) increased in Examples 1-1 and 1-2 using infrared heating. That is, it was found that Examples 1-1 and 1-2 were able to produce the gas barrier polymer layer 103 having an amide crosslinked structure more efficiently than Comparative Example 1. Further, it was found that such a gas barrier laminate film has a low oxygen permeability and is superior in gas barrier performance.
Further, from the comparative examples with Examples 2-1 and 2-2 and Comparative Example 2 having the same heat treatment time and temperature, and the comparative examples with Example 3 and Comparative Example 3, heating means for the coating layer It was found that the ratio of the amide bond (B / A) was higher in the example using a hot roll or far infrared heating than in the comparative example using only a hot air dryer.
From the above, it has been found that according to the production method of the present invention, a gas barrier laminate excellent in gas barrier performance can be produced efficiently.

  This application claims the priority on the basis of Japanese application Japanese Patent Application No. 2015-103500 for which it applied on May 21, 2015, and takes in those the indications of all here.

Claims (7)

A gas barrier laminate manufacturing method comprising: a base material layer; and a gas barrier polymer layer provided on at least one surface of the base material layer,
Applying a mixture containing a polycarboxylic acid and a polyamine compound to a base material layer to obtain a coating layer;
The coating layer is heated by a heating means, and a gas barrier polymer layer having an amide bond is formed by dehydration condensation reaction between a carboxyl group contained in the polycarboxylic acid and an amino group contained in the polyamine compound. Process,
Including
The manufacturing method of the gas-barrier laminated body in which the said heating means contains at least 1 type selected from a conduction heat transfer system and a radiation heat transfer system.   The method for producing a gas barrier laminate according to claim 1, wherein the heating means includes at least one selected from conductive heat transfer by a heating roll and radiation heat transfer by infrared rays.   The manufacturing method of the gas-barrier laminated body of Claim 1 or 2 with which the said heating means further contains a convection heat transfer system. In the step of forming the gas barrier polymer layer,
In the infrared absorption spectrum of the gas barrier polymer layer obtained,
The total peak area in the range of the absorption band 1493 cm ^{−1 to} 1780 cm ⁻¹ is A,
When the total peak area in the range of the absorption band 1598cm ^-1 or 1690 cm ^-1 and is B,
The manufacturing method of the gas-barrier laminated body as described in any one of Claims 1 thru | or 3 which heats until the area ratio of the amide bond shown by B / A becomes 0.330 or more.   (The number of moles of —COO— groups contained in the polycarboxylic acid in the mixture) / (the number of moles of amino groups contained in the polyamine compound in the mixture) = over 100/22 and up to 100/99, The manufacturing method of the gas-barrier laminated body as described in any one of Claims 1 thru | or 4.   The said polycarboxylic acid contains the polymer of 1 type, or 2 or more types selected from the copolymer of polyacrylic acid, polymethacrylic acid, and acrylic acid and methacrylic acid, The Claim 1 thru | or 5 characterized by the above-mentioned. A method for producing a gas barrier laminate.   The method for producing a gas barrier laminate according to any one of claims 1 to 6, wherein the polyamine compound comprises polyethyleneimine.

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