JP6862815B2 - Manufacturing method and molded product of gas barrier laminate for thermoforming, coating liquid, gas barrier laminate for thermoforming - Google Patents

Description

The present invention relates to a coating liquid, a gas barrier laminate for thermoforming, and a molded product.

A gas barrier film is known in which a coating liquid containing ultrafine particles of a polyvalent metal compound such as zinc oxide is coated on a layer containing a polycarboxylic acid-based polymer. Such a gas barrier film has excellent gas barrier properties by being subjected to heat sterilization treatment such as retort treatment and boiling treatment.
Patent Document 1 proposes a coating liquid containing zinc oxide ultrafine particles, a polyester resin, sodium polycarboxylic acid, and water. Since this coating liquid uses a sodium polycarboxylic acid salt as a dispersant, it is said that the dispersibility of the zinc oxide ultrafine particles is good. A gas barrier laminate having a layer formed from this coating liquid and a layer containing polyacrylic acid is said to be excellent in transparency and gas barrier properties.

International Publication No. 2010/061705

However, the gas barrier laminate having a layer formed from the coating liquid and a layer containing a polycarboxylic acid-based polymer proposed in Patent Document 1 is thermoformed into a container shape or the like and then heat sterilized. Gas barrier property is not sufficient (thermoforming property is insufficient). Therefore, this gas barrier laminate cannot be applied to a molded container or the like.
By incorporating a resin such as a thermoplastic resin or a thermosetting resin into the coating liquid, stretchability is imparted to the gas barrier laminate having a layer formed from this coating liquid and a layer containing polyacrylic acid, and heat is imparted. It is conceivable to improve moldability. However, most of these resins are non-aqueous solvent systems that are insoluble in water and soluble in non-aqueous solvents. When a non-aqueous solvent-based resin is mixed with the above-mentioned coating liquid in which water is used as a liquid medium for dispersing zinc oxide ultrafine particles and dissolving sodium polycarboxylic acid, a problem such as resin precipitation occurs and the coating liquid is used. It is difficult to make the product itself. Therefore, it is difficult to apply a non-aqueous solvent-based resin to the coating liquid.

The present invention has been made in view of the above circumstances, and even if the liquid medium is a non-aqueous medium, the dispersibility of the zinc oxide ultrafine particles is good, and a gas barrier laminate having excellent thermoformability can be produced. It is an object of the present invention to provide a coating liquid.
The present invention also provides a gas barrier laminate for thermoforming, which has a layer in which zinc oxide ultrafine particles are uniformly distributed as small particles and has excellent thermoforming properties, and a molded product using the same. For other purposes.

As a result of intensive research to achieve the above object, the present inventors have used a vinyl acetate unit-containing resin as a dispersant, so that even when a non-aqueous medium is used as a liquid medium, zinc oxide ultrafine particles are used. We have found that a coating liquid having good dispersibility can be obtained, and have completed the present invention.

The present invention has the following aspects.
<1> Zinc oxide ultrafine particles, a polyester resin, a vinyl acetate unit-containing resin, and a liquid medium are included, and the content of the zinc oxide ultrafine particles is based on the total mass of the total solid content in the coating liquid. A coating liquid having a content of 20 to 90% by mass and a content of the vinyl acetate unit-containing resin of 1 to 40 parts by mass with respect to 100 parts by mass of the zinc oxide ultrafine particles.
<2> The coating liquid according to <1>, wherein the liquid medium is an organic solvent.
<3> A gas barrier laminate for thermal molding having a base material and a gas barrier layer formed on the base material, wherein the gas barrier layer is made of zinc oxide ultrafine particles, a polyester resin, and a vinyl acetate unit. It has a layer (A) containing a resin and a layer (B) containing a polycarboxylic acid-based polymer, and the content of the zinc oxide ultrafine particles is 20 with respect to the total mass of the layer (A). A gas barrier laminate for thermal molding, which is ~ 90% by mass and the content of the vinyl acetate unit-containing resin is 1 to 40 parts by mass with respect to 100 parts by mass of the zinc oxide ultrafine particles.
<4> The gas barrier laminate for thermoforming according to <3>, wherein the layer (A) is a layer formed from the coating liquid according to <1> or <2>.
<5> A molded product using the gas barrier laminate for thermoforming according to the above <3> or <4>.

The coating liquid of the present invention has good dispersibility of zinc oxide ultrafine particles even when the liquid medium is non-aqueous, and can produce a gas barrier laminate having excellent thermoformability.
The gas barrier laminate of the present invention has a layer in which zinc oxide ultrafine particles are uniformly distributed as small particles, and is excellent in thermoformability. Therefore, the molded product of the present invention using this is suppressed from being lowered in gas barrier property due to thermoforming, and has excellent gas barrier property.

It is sectional drawing which shows typically the gas-barrier laminate for thermoforming of 1st Embodiment of this invention. It is sectional drawing which shows typically the gas barrier laminated body for thermoforming of the 2nd Embodiment of this invention. It is sectional drawing which shows typically the gas barrier laminated body for thermoforming of the 3rd Embodiment of this invention. It is a top view which shows the molded article (round molding container) of the 4th Embodiment of this invention. It is a VV cross-sectional view of the molded article shown in FIG.

Hereinafter, embodiments of the coating liquid, the gas barrier laminate for thermoforming, and the molded product of the present invention will be described. However, the present embodiment is specifically described in order to better understand the gist of the invention, and is not limited to the present invention unless otherwise specified.

≪Coating liquid≫
The coating liquid of the present invention (hereinafter, also referred to as coating liquid (a)) includes zinc oxide ultrafine particles, a polyester resin, a vinyl acetate unit-containing resin, and a liquid medium.
The coating liquid (a) may further contain components other than the above-mentioned zinc oxide ultrafine particles, polyester resin, vinyl acetate unit-containing resin and liquid medium, if necessary.

<Zinc oxide ultrafine particles>
In the present invention, the "ultrafine particles" mean particles having an average primary particle size of 1 nm to 1000 nm measured by a laser diffraction / scattering method.
The average primary particle size of the zinc oxide ultrafine particles is preferably 200 nm or less, more preferably 150 nm or less, and particularly preferably 100 nm or less. The average primary particle size of the zinc oxide ultrafine particles is preferably 5 nm or more. When the average primary particle size of the zinc oxide ultrafine particles is not more than the above upper limit value, the dispersibility of the zinc oxide ultrafine particles in the coating liquid (a) is excellent and the liquid stability is good. Further, the transparency of the layer obtained by applying the coating liquid (a) to a base material such as a film and drying it is excellent.
Therefore, the average primary particle size of the zinc oxide ultrafine particles is preferably 5 to 200 nm, more preferably 5 to 150 nm, and particularly preferably 5 to 100 nm.

Commercially available products may be used as the zinc oxide ultrafine particles. Examples of commercially available zinc oxide ultrafine particles include FINEX50 (manufactured by Sakai Chemical Industry Co., Ltd., average primary particle size 20 nm), ZINCOX SUPER F-2 (manufactured by HakusuiTech Co., Ltd., average primary particle size 65 nm) and the like.

<Polyester resin>
As the polyester-based resin, a thermoplastic resin, a thermosetting resin, or the like, and a polyester-based resin used in the adhesive field or the paint field can be preferably used.

The number average molecular weight of the polyester resin is preferably 1,000 to 200,000, more preferably 5,000 to 100,000, and particularly preferably 10,000 to 100,000. When the number average molecular weight is within the above range, the thermoformability of the layer formed from the coating liquid (a) is more excellent.

<Vinyl acetate unit-containing resin>
The vinyl acetate unit-containing resin is a polymer containing vinyl acetate units. The vinyl acetate unit-containing resin may be a homopolymer of vinyl acetate, or may be a copolymer (copolymer resin) of vinyl acetate and a monomer other than vinyl acetate.
As the vinyl acetate unit-containing resin, various vinyl acetate unit-containing resins used in the adhesive field and the paint field can be preferably used.

When the vinyl acetate unit-containing resin is a copolymer resin, the vinyl acetate unit-containing resin further contains other monomer units other than the vinyl acetate unit. Examples of the other monomer unit include a vinyl chloride unit, an ethylene unit, a vinyl alcohol unit, a hydroxyalkyl acrylate unit, a dicarboxylic acid unit and the like.
A particularly preferable copolymer resin is a vinyl chloride / vinyl acetate copolymer resin containing a vinyl acetate unit and a vinyl chloride unit. As the vinyl chloride / vinyl acetate copolymer resin, the vinyl chloride / vinyl acetate copolymer resin used in the adhesive field and the paint field can be preferably used.

The number average molecular weight of the vinyl acetate unit-containing resin is preferably 300,000 or less, more preferably 200,000 or less. When the number average molecular weight is within the above range, the dispersibility of the zinc oxide ultrafine particles in the coating liquid (a) is more excellent.

<Liquid medium>
As the liquid medium, a liquid medium other than water is usually used, and an organic solvent is preferable. Examples of the organic solvent include ethyl acetate, ethylene glycol monobutyl ether, toluene, methyl ethyl ketone, ethyl alcohol, isopropyl alcohol and the like. One of these organic solvents may be used alone, or two or more thereof may be used in combination.

<Other ingredients>
Examples of other components include a curing agent, an anti-blocking agent, and the like.
As the curing agent, a known curing agent such as polyisocyanate can be used.

<Contents of each component in the coating liquid (a)>
The solid content concentration of the coating liquid (a) is preferably 3 to 30% by mass, more preferably 5 to 20% by mass. When the solid content concentration is within the above range, the coatability and liquid stability are good.
The solid content concentration of the coating liquid (a) is the ratio of the solid content amount to the total amount (100% by mass) of the coating liquid (a).
The solid content of the coating liquid (a) is the total mass of the total solid content in the coating liquid (a). That is, the total mass of the zinc oxide ultrafine particles in the coating liquid (a), the polyester resin, the vinyl acetate unit-containing resin, and the solid of the other components (the solid of the other components). Including the case where does not include.).

The content of the zinc oxide ultrafine particles in the coating liquid (a) is 20 to 90% by mass, preferably 30 to 80% by mass, based on the solid content (100% by mass). When the content of the zinc oxide ultrafine particles is within the above range, the gas barrier property for thermoforming having a layer formed from the coating liquid (a) and the molded product thereof are excellent.

The content of the polyester resin in the coating liquid (a) is preferably 2 to 80% by mass, more preferably 5 to 50% by mass, based on the solid content (100% by mass). When the content of the polyester resin is within the above range, the stretchability of the thermoforming gas barrier laminate having the layer formed from the coating liquid (a) is more excellent.

The content of the vinyl acetate unit-containing resin in the coating liquid (a) is 1 to 40 parts by mass, preferably 2 to 30 parts by mass, with respect to 100 parts by mass of the zinc oxide ultrafine particles. When the content of the vinyl acetate unit-containing resin is within the above range, the dispersibility of the zinc oxide ultrafine particles is good, and the liquid stability of the coating liquid (a) is excellent. Further, the gas barrier laminate for thermoforming having a layer formed from the coating liquid (a) and the molded product thereof are excellent in gas barrier property and heat resistance.

The content of the vinyl acetate unit-containing resin in the coating liquid (a) is preferably 0.6 to 24% by mass, more preferably 1.2 to 18% by mass, based on the solid content (100% by mass). When the content of the vinyl acetate unit-containing resin is within the above range, the dispersibility of the zinc oxide ultrafine particles is good, and the liquid stability of the coating liquid (a) is excellent. Further, the gas barrier laminate for thermoforming having a layer formed from the coating liquid (a) and the molded product thereof are excellent in gas barrier property and heat resistance.

The content of the solid component among the other components in the coating liquid (a) is preferably less than 10% by mass, more preferably less than 8% by mass, based on the solid content (100% by mass). That is, the total amount of the zinc oxide ultrafine particles, the polyester resin, and the vinyl acetate unit-containing resin in the coating liquid (a) is preferably 90% by mass or more, preferably 92% by mass, based on the solid content (100% by mass). The above is more preferable.

<Preparation method of coating liquid (a)>
The method for preparing the coating liquid (a) is not particularly limited, and the coating liquid (a) is prepared by mixing zinc oxide ultrafine particles, a polyester resin, a vinyl acetate unit-containing resin, a liquid medium, and if necessary, other components. a) can be obtained.
The mixing order of each material is not particularly limited. The mixing method of each material is not particularly limited as long as each of the above-mentioned components can be mixed so as to be uniform.

As an example of the method for preparing the coating liquid (a), zinc oxide ultrafine particles and a vinyl acetate unit-containing resin are added to an organic solvent to crush and disperse the agglomeration of the primary particles of the zinc oxide ultrafine particles to disperse zinc oxide. Examples thereof include a method of obtaining a dispersion of ultrafine particles, adding a polyester resin to the dispersion of ultrafine particles of zinc oxide and stirring the mixture to obtain a coating liquid (a).
A bead mill, a high-speed stirrer, or the like can be used to crush the agglomerates when obtaining the dispersion of the zinc oxide ultrafine particles. In particular, when a bead mill is used, the haze of the obtained gas barrier laminate for thermoforming tends to be small, which is preferable.

<Effect>
The coating liquid (a) of the present invention contains zinc oxide ultrafine particles, a polyester resin, a vinyl acetate unit-containing resin, and a liquid medium, and the content of the zinc oxide ultrafine particles is relative to the solid content. Since the content of the vinyl acetate unit-containing resin of 20 to 90% by mass is 1 to 40 parts by mass with respect to 100 parts by mass of the zinc oxide ultrafine particles, the dispersion stability of the zinc oxide ultrafine particles is good.
Further, the layer formed from the coating liquid (a) is combined with a layer containing a polycarboxylic acid-based polymer to form a gas barrier layer. The thermoforming gas barrier laminate having such a gas barrier layer has high thermoforming property, and is thermoformed by stretching such as forming a container shape, and then heat sterilized by retort treatment, boiling treatment, etc. After performing the above, it exhibits excellent gas barrier properties.
The reason for achieving the above effect is that by using a vinyl acetate unit-containing resin as a dispersant for the zinc oxide ultrafine particles, the dispersed state of the zinc oxide ultrafine particles in the coating liquid (a) remains smaller. It can be held stably, whereby zinc oxide ultrafine particles are uniformly distributed as small particles in the layer formed from the coating liquid, and the state is sufficiently maintained even after thermoforming.
Since the zinc oxide ultrafine particles are uniformly distributed as small particles, the reaction between zinc oxide and the polycarboxylic acid-based polymer (polycarboxylic acid-based) uniformly over the entire in-plane direction of the gas barrier layer during heat sterilization treatment. Ion cross-linking with zinc ions of the polymer) occurs, and it is considered that the reaction is more likely to proceed.
When a vinyl acetate unit-containing resin is not used as the dispersant, the dispersibility of the zinc oxide ultrafine particles deteriorates, the zinc oxide ultrafine particles aggregate during the preparation of the coating liquid, and the particle size of the zinc oxide ultrafine particles increases. It is considered that the liquid stability of the coating liquid deteriorates and it becomes difficult to prepare the liquid.

[Gas barrier laminate for thermoforming]
An embodiment of the gas barrier laminate for thermoforming of the present invention will be described.

<< First Embodiment >>
FIG. 1 is a cross-sectional view schematically showing a gas barrier laminate 10 for thermoforming according to the first embodiment of the present invention.
The thermoforming gas barrier laminate 10 includes a base material 1 and a gas barrier layer 2 provided on the base material 1.
The gas barrier layer 2 has a layer (A) 4 and a layer (B) 3. The layer (A) 4 is laminated on the side of the layer (B) 3 opposite to the base material 1 side.

<Base material>
The base material 1 is thermoformed and serves as a support for laminating layers (A) 4, layers (B) 3, and the like.
The material constituting the base material 1 is not particularly limited, but when the thermoforming gas barrier laminate 10 is used as a packaging material, a polyester polymer, a polyamide polymer, or the like, from the viewpoint of suitability as a packaging material, Polyolefin-based polymers are preferred.
Examples of the polyester-based polymer include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyε-caprolactone, polyhydroxybutyrate, polyhydroxyvariate, and copolymers thereof. Examples of the polyamide-based polymer include nylon 6, nylon 66, nylon 12, nylon 6,66 copolymer, nylon 6,12 copolymer, metaxylene adipamide / nylon 6 copolymer, and copolymers thereof. Can be mentioned. Examples of the polyolefin-based polymer include low-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, poly4-methylpentene, cyclic polyolefins, copolymers thereof, and acid-modified products thereof.

The form of the base material 1 is not particularly limited, but can be used in the form of an unstretched sheet, an unstretched film, or the like.
The base material 1 may be composed of a single layer or may be composed of a plurality of layers.
The surface of the base material 1 may be subjected to surface activation treatment such as corona treatment, flame treatment, and plasma treatment.
The thickness of the base material 1 is not particularly limited, but is preferably in the range of 5 to 500 μm, and more preferably in the range of 10 to 300 μm. If the thickness of the base material 1 is less than the lower limit of the above range, problems with coatability such as easy cutting of the base material 1 tend to occur, while if the thickness exceeds the upper limit of the above range, the rigidity of the base material 1 tends to increase. Because it is too high, it tends to cause problems in handleability in secondary processing and filling of contents.

<Layer (A)>
Layer (A) 4 contains zinc oxide ultrafine particles, a polyester-based resin, and a vinyl acetate unit-containing resin. The layer (A) 4 may further contain components other than the zinc oxide ultrafine particles, the polyester resin, the vinyl acetate unit-containing resin, and the liquid medium, if necessary.
The zinc oxide ultrafine particles, the polyester resin, the vinyl acetate unit-containing resin, and the other components are the same as those described in the description of the coating liquid (a), and the preferred embodiments are also the same.

The content of the zinc oxide ultrafine particles in the layer (A) 4 is 20 to 90% by mass, preferably 30 to 80% by mass, based on the total mass (100% by mass) of the layer (A) 4. When the content of the zinc oxide ultrafine particles is within the above range, the gas barrier property of the thermoforming gas barrier laminate 10 and the molded product thereof is excellent.

The content of the polyester resin in the layer (A) 4 is preferably 2 to 80% by mass, more preferably 5 to 50% by mass, based on the total mass (100% by mass) of the layer (A) 4. When the content of the polyester resin is within the above range, the stretchability of the thermoforming gas barrier laminate 10 is more excellent.

The content of the vinyl acetate unit-containing resin in the layer (A) 4 is 1 to 40 parts by mass, preferably 2 to 30 parts by mass, based on 100 parts by mass of the zinc oxide ultrafine particles. When the content of the vinyl acetate unit-containing resin is within the above range, the zinc oxide ultrafine particles are uniformly distributed in the layer (A) 4 as small particles, and the gas barrier laminate 10 for thermoforming and the gas barrier of the molded product thereof. Excellent properties and heat resistance.

The content of the vinyl acetate unit-containing resin in the layer (A) 4 is preferably 0.6 to 24% by mass, preferably 1.2 to 18% by mass, based on the total mass (100% by mass) of the layer (A) 4. Is more preferable. When the content of the vinyl acetate unit-containing resin is within the above range, the zinc oxide ultrafine particles are uniformly distributed in the layer (A) 4 as small particles, and the gas barrier laminate 10 for thermoforming and the gas barrier of the molded product thereof. Excellent properties and heat resistance.

The content of the solid component among the other components in the layer (A) 4 is preferably less than 10% by mass, more preferably less than 8% by mass, based on the total mass (100% by mass) of the layer (A) 4. preferable. That is, the total amount of the zinc oxide ultrafine particles, the polyester resin, and the vinyl acetate unit-containing resin in the layer (A) 4 is 90% by mass or more with respect to the total mass (100% by mass) of the layer (A) 4. It is preferable, and more preferably 92% by mass or more.

The layer (A) 4 is typically a layer formed from the coating liquid (a).
The method for forming the layer (A) 4 using the coating liquid (a) will be described in detail later.
When the layer (A) 4 is a layer formed from the coating liquid (a), the content of the zinc oxide ultrafine particles with respect to the total mass of the layer (A) 4 is usually the solid content of the coating liquid (a). Is equal to the content of zinc oxide ultrafine particles. The same applies to the contents of the polyester resin, the vinyl acetate unit-containing resin, and other components.

The thickness of the layer (A) 4 (thickness of the gas barrier laminate 10 for thermoforming before thermoforming) is preferably in the range of 0.05 to 50 μm, preferably in the range of 0.1 to 10 μm. It is more preferable to be in the range of 0.2 to 5 μm, and particularly preferably in the range of 0.2 to 5 μm. If the thickness of the layer (A) 4 is less than the lower limit of the above range, the gas barrier property of the thermoforming gas barrier laminate 10 and the molded body tends to be insufficient, while if the thickness exceeds the upper limit of the above range, heat tends to be insufficient. Moldability tends to be poor.

<Layer (B)>
Layer (B) 3 contains a polycarboxylic acid-based polymer.
Layer (B) 3 contains at least one silicon-containing compound (i) selected from the group consisting of a silane coupling agent, a hydrolyzate thereof, and a condensate thereof from the viewpoint of gas barrier properties and heat resistance and water resistance. Is preferable.
The layer (B) 3 preferably contains a plasticizer (ii) from the viewpoint of stretchability.
If necessary, the layer (B) 3 may further contain components other than the polycarboxylic acid-based polymer, the silicon-containing compound (i), and the plasticizer (ii).

(Polycarboxylic acid polymer)
The polycarboxylic acid-based polymer refers to a polymer having two or more carboxyl groups in one molecule.
Examples of the polycarboxylic acid-based polymer include (co) polymers of ethylenically unsaturated carboxylic acids; copolymers of ethylenically unsaturated carboxylic acids and other ethylenically unsaturated monomers; alginic acid, carboxymethyl cellulose, and the like. Examples thereof include acidic polysaccharides having a carboxyl group in the molecule such as ethylene.

Examples of the ethylenically unsaturated carboxylic acid include acrylic acid, methacrylic acid, crotonic acid, vinyl lactic acid, maleic acid, fumaric acid, aconitic acid, itaconic acid, mesaconic acid, citraconic acid, and methylene malonic acid. Ethylene unsaturated carboxylic acids having 3 to 5 carbon atoms (C3 to C5) such as acrylic acid and methacrylic acid are preferable.
Other ethylenically unsaturated monomers copolymerizable with the ethylenically unsaturated carboxylic acid include, for example, acrylamide, methacrylicamide, acrylonitrile, methyl acrylate, ethyl acrylate, methyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate. C3-C5 ethylenically unsaturated carboxylic acid amides, nitriles or esters, or vinyl acetate, 2-acrylamide-2-methylpropanesulfonic acid, vinylsulfonic acid, ethylene, propylene, styrene, α-methylstyrene, Examples include nuclear methyl-substituted styrene.

As the polycarboxylic acid-based polymer, poly (meth) acrylic acid is preferable.
The poly (meth) acrylic acid referred to here is a polymer having two or more (meth) acrylic acid units. The (meth) acrylic acid unit indicates one or both of an acrylic acid unit and a methacrylic acid unit.
Examples of the poly (meth) acrylic acid include the following.
Acrylic acid or methacrylic acid homopolymer (polyacrylic acid, polymethacrylic acid),
Copolymer of acrylic acid and methacrylic acid,
(Meta) acrylic acid and ethylenically unsaturated carboxylic acids other than (meth) acrylic acid (crotonic acid, vinyl lactic acid, maleic acid, fumaric acid, aconitic acid, itaconic acid, mesaconic acid, citraconic acid, methylenemalonic acid, etc.) Copolymer with,
A copolymer of (meth) acrylic acid and another ethylenically unsaturated monomer copolymerizable with an ethylenically unsaturated carboxylic acid,
A copolymer of (meth) acrylic acid, an ethylenically unsaturated carboxylic acid other than (meth) acrylic acid, and another ethylenically unsaturated monomer copolymerizable with the ethylenically unsaturated carboxylic acid.

When the poly (meth) acrylic acid has an ethylenically unsaturated carboxylic acid unit other than the (meth) acrylic acid, the ratio of the ethylenically unsaturated carboxylic acid unit in the poly (meth) acrylic acid is not particularly limited. It may be any ratio.
When the poly (meth) acrylic acid has another ethylenically unsaturated monomeric unit copolymerizable with the ethylenically unsaturated carboxylic acid, that is, a unit having no carboxyl group, the poly (meth) acrylic acid in the poly (meth) acrylic acid. The proportion of the other ethylenically unsaturated monomeric unit is set within a range that does not inhibit the water solubility of poly (meth) acrylic acid, and is preferably 20% by mass based on the total mass (100% by mass) of all the units. It is as follows.

Poly (meth) acrylic acid is a method of polymerizing (meth) acrylic acid, and if necessary, an ethylenically unsaturated carboxylic acid other than (meth) acrylic acid, and other ethylenically unsaturated monomers. Meta) It can be produced by a method of saponifying an acrylic acid ester or the like. The polymerization method is not particularly limited, and known polymerization methods such as bulk polymerization, aqueous solution polymerization, polymerization in an organic solvent, and irradiation polymerization can be used. Any one produced by any method can be applied to the present invention. When the layer (B) is formed by using the coating liquid (b), the polycarboxylic acid-based polymer is usually used as an aqueous solution, so that aqueous solution polymerization is industrially advantageous.

The polycarboxylic acid-based polymer may be partially neutralized with a monovalent metal compound and / or a divalent metal compound. Examples of the metal contained in such a metal compound include sodium, calcium, zinc and the like. Examples of such a metal compound include sodium hydroxide, calcium hydroxide, calcium oxide, zinc oxide and the like.
The amount of the metal compound added is not particularly limited as long as it does not impair the stretch moldability, but is preferably 0.3 chemical equivalent or less with respect to the content of the carboxyl group of the polycarboxylic acid.

The number average molecular weight of the polycarboxylic acid-based polymer is preferably in the range of 10,000 to 1,000,000 from the viewpoint of the formability of the organic thin film, and is in the range of 50,000 to 1,000,000. It is more preferable to be inside. If it is less than the lower limit of the above range, the thermoforming property of the obtained gas barrier laminate for thermoforming tends to be poor, and if it exceeds the upper limit of the above range, the formability of the thin film tends to be impaired.

(Silicon-containing compound (i))
The silicon-containing compound (i) comprises at least one compound selected from the group consisting of a silane coupling agent, a hydrolyzate thereof, and a condensate thereof. By using the silicon-containing compound (i), the gas barrier property becomes more excellent. Further, since heat-resistant water can be imparted without impairing moldability, the frequency of occurrence of delamination during the heat sterilization treatment can be reduced, and excellent gas barrier properties can be maintained even after the heat sterilization treatment.

Examples of the silane coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-isocyanatepropyltri. Examples thereof include methoxysilane and γ-isocyanatepropyltriethoxysilane. Among these, γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropyltriethoxysilane are preferable.

The silicon-containing compound (i) may be the silane coupling agent itself, a hydrolyzate obtained by hydrolyzing the silane coupling agent, or a condensate thereof.
As the silicon-containing compound (i), for example, a compound obtained by hydrolyzing and condensing a silane coupling agent using a sol-gel method can be used.
When the silane coupling agent is hydrolyzed, at least a part of the alkoxy group (OR) bonded to the silicon atom of the silane coupling agent is replaced with a hydroxyl group to become a hydrolyzate. Further, the hydrolyzate is condensed to form a compound in which silicon atoms (Si) are bonded via oxygen. By repeating this condensation, a hydrolyzed condensate is obtained.

Normally, a silane coupling agent easily hydrolyzes, and a condensation reaction easily occurs in the presence of an acid or an alkali. Therefore, only the silane coupling agent, its hydrolyzate only, or a condensate thereof. It rarely exists only. That is, the silicon-containing compound (i) is often a mixture of a silane coupling agent, a hydrolyzate thereof, and a condensate thereof. In addition, the hydrolyzate often includes a partial hydrolyzate and a complete hydrolyzate.
The silicon-containing compound (i) preferably contains at least a hydrolyzed condensate.

When the layer (B) contains the silicon-containing compound (i), the content of the silicon-containing compound (i) is the mass of the polycarboxylic acid-based polymer from the viewpoint of the gas barrier property of the gas-barrier laminate 10 for thermal molding. The ratio of the weight of the silicon-containing compound (i) to the mass of the silicon-containing compound (i) (polycarboxylic acid-based polymer / silicon-containing compound (i)) is 99.5 / 0.5 to 80.0 / 20.0. preferable.
However, the mass of the silicon-containing compound (i) other than the silane coupling agent is the mass in terms of the silane coupling agent. That is, the silicon-containing compound (i) is usually a mixture of a silane coupling agent, a hydrolyzate thereof, and a condensate thereof, but the mass of the silicon-containing compound (i) is a silane coupling agent. The converted value, that is, the amount of the silane coupling agent charged.

(Plasticizer (ii))
As the plasticizer (ii), it is possible to appropriately select and use from known materials.
Specific examples of the plasticizer (ii) include ethylene glycol, trimethylene glycol, propylene glycol, tetramethylene glycol, 1,3-butanediol, 2,3-butanediol, pentamethylene glycol, hexamethylene glycol, and diethylene glycol. , Triethylene glycol, polyethylene glycol, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyethylene oxide, sorbitol, mannitol, dulcitol, erythritol, glycerin, polyglycerin, lactic acid, fatty acid, starch, phthalate ester and the like. Among these, glycerin, polyglycerin, ethylene glycol, polyethylene glycol and the like are preferable from the viewpoint of the thermoformability of the thermoforming gas barrier laminate 10 and the gas barrier property of the molded product. These materials may be used alone or in combination of two or more.

When the layer (B) contains a plasticizer (ii), the content of the plasticizer (ii) is the ratio of the mass of the polycarboxylic acid-based polymer to the mass of the plasticizer (ii) (polycarboxylic acid-based weight). The amount of the coalesced / silicon-containing compound (i)) is preferably 95/5 to 80/20, and more preferably 95/5 to 85/15. When the ratio is within the above range, both the thermoforming property of the thermoforming gas barrier laminated body 10 and the gas barrier property of the molded body can be compatible. That is, since the polycarboxylic acid-based polymer is sufficiently present in the layer (B) 3, it is derived from the polycarboxylic acid-based polymer in the layer (B) 3 and the zinc oxide ultrafine particles in the layer (A). It is possible to form an ionic bond with the zinc ion to develop a stable gas barrier property. Further, when the plasticizer (ii) is sufficiently present in the layer (B) 3, more excellent stretchability can be imparted to the layer (B) 3, and the thermoformability is further excellent.

The layer (B) 3 is typically a layer formed from a coating liquid (b) containing a polycarboxylic acid-based polymer and a liquid medium.
The coating liquid (b) and the method for forming the layer (B) 3 using the coating liquid (b) will be described in detail later.

The thickness of the layer (B) 3 (thickness of the gas barrier laminate 10 for thermoforming before thermoforming) is preferably in the range of 0.01 to 20 μm, preferably in the range of 0.05 to 10 μm. It is more preferable, and it is particularly preferable that it is in the range of 0.1 to 5 μm. If the thickness of layer (B) 3 is less than the lower limit of the above range, film formation tends to be difficult, while if it exceeds the upper limit of the above range, the ionic bonding reaction with zinc ions becomes uniform in the thickness direction. Since it becomes difficult to proceed, the gas barrier property of the obtained molded product tends to be insufficient.

<Coating liquid (b)>
The coating liquid (b) contains a polycarboxylic acid-based polymer and a liquid medium.
The coating liquid (b) contains at least one silicon-containing compound (i) selected from the group consisting of a silane coupling agent, a hydrolyzate thereof, and a condensate thereof from the viewpoint of gas barrier properties and heat resistance and water resistance. Is preferable.
The coating liquid (b) preferably contains a plasticizer (ii) from the viewpoint of stretchability.
The coating liquid (b) may further contain components other than the polycarboxylic acid-based polymer, the silicon-containing compound (i), the plasticizer (ii), and the liquid medium, if necessary.

The polycarboxylic acid-based polymer, the silicon-containing compound (i), the plasticizer (ii), and the other components are the same as those mentioned in the description of the layer (B), and the preferred embodiments are also the same.

The liquid medium of the coating liquid (b) is not particularly limited except that water for carrying out the hydrolysis reaction is usually required when the silane coupling agent is contained, and water and an organic solvent are used. , A mixed solvent of water and an organic solvent or the like can be used.
As the liquid medium, water is preferable in terms of solubility and cost of the polycarboxylic acid polymer, and alcohol and the like are used in terms of improving the solubility of the silane coupling agent and the coatability of the coating liquid (b). Organic solvents are preferred. Therefore, a mixed solvent of water and an organic solvent is particularly preferable.

As the water, purified water is preferable, and for example, distilled water, ion-exchanged water, or the like can be used.
As the organic solvent, it is preferable to use at least one organic solvent selected from the group consisting of lower alcohols having 1 to 5 carbon atoms and lower ketones having 3 to 5 carbon atoms.
Specific examples of the organic solvent include methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, acetone, methyl ethyl ketone and the like.

As the mixed solvent of water and an organic solvent, the above-mentioned mixed solvent using water or an organic solvent is preferable, and a mixed solvent of water and a lower alcohol having 1 to 5 carbon atoms is more preferable.
In the mixed solvent, water may be present in an amount of 20 to 95% by mass and an organic solvent may be present in an amount of 80 to 5% by mass (however, the total of water and the organic solvent is 100% by mass). preferable.

When the coating liquid (b) contains the silicon-containing compound (i), the ratio of the mass of the polycarboxylic acid-based polymer to the mass of the silicon-containing compound (i) (polycarboxylic acid-based polymer / silicon-containing compound (i). )) Is preferably 99.5 / 0.5 to 80.0 / 20.0 from the viewpoint of the gas barrier property of the thermoforming gas barrier laminate 10.
However, the mass of the silicon-containing compound (i) other than the silane coupling agent is the mass in terms of the silane coupling agent. That is, the silicon-containing compound (i) is usually a mixture of a silane coupling agent, a hydrolyzate thereof, and a condensate thereof, but the mass of the silicon-containing compound (i) is a silane coupling agent. The converted value, that is, the amount of the silane coupling agent charged.

When the coating liquid (b) contains the plasticizer (ii), the ratio of the mass of the polycarboxylic acid-based polymer to the mass of the plasticizer (ii) (polycarboxylic acid-based polymer / silicon-containing compound (i)). Is preferably 95/5 to 80/20, and more preferably 95/5 to 85/15. When the ratio is within the above range, both the thermoforming property of the thermoforming gas barrier laminated body 10 and the gas barrier property of the molded body can be compatible.

The solid content concentration of the coating liquid (b) is preferably 0.5 to 50% by mass, more preferably 0.8 to 30% by mass, and 1.0 to 20% by mass from the viewpoint of gas barrier property and coatability. Especially preferable.
The solid content concentration of the coating liquid (b) is the ratio of the solid content amount to the total amount (100% by mass) of the coating liquid (b).
The solid content of the coating liquid (b) is the total mass of the total solid content in the coating liquid (b). That is, it is the total mass of the polycarboxylic acid-based polymer in the coating liquid (b) and the additives (silicon-containing compound (i), plasticizer (ii), and other components) contained as needed.

When the layer (B) 3 is a layer formed from the coating liquid (b), the content of the polycarboxylic acid-based polymer with respect to the total mass of the layer (B) 3 is usually that of the coating liquid (b). It is equal to the content of the polycarboxylic acid-based polymer with respect to the solid content. The same applies to the contents of the silicon-containing compound (i), the plasticizer (ii), and the other components.

<Use>
The thermoforming gas barrier laminate 10 is used for thermoforming. In the present specification and claims, "thermoforming" means molding with stretching of a gas barrier laminate for thermoforming under heating.
The gas barrier laminate 10 for thermoforming is made into a molded product by thermoforming. For example, a thermoformed gas barrier laminate 10 is heated, and in that state, the thermoforming gas barrier laminate 10 is stretched and molded into an arbitrary shape to obtain a molded product. Such a molded product includes a gas barrier laminate 10 for thermoforming in which at least a part thereof is stretched. Examples of molded products include molded containers, bags and the like.

<Manufacturing method of gas barrier laminate for thermoforming of the first embodiment>
Examples of the method for producing the thermoforming gas barrier laminate 10 include a production method including the following steps (α1) and (α2).
(Α1): A step of forming the layer (B) 3 on one surface of the base material 1.
(Α2): A step of forming the layer (A) 4 on the surface of the base material 1 on the side on which the layer (B) 3 is formed.

(Process (α1))
The method for forming the layer (B) is not particularly limited, and examples thereof include a method in which the coating liquid (b) is applied onto the base material 1 and dried.

The coating method of the coating liquid (b) is not particularly limited, and for example, a casting method, a dipping method, a roll coating method, a gravure coating method, a screen printing method, a reverse coating method, a spray coating method, a kit coating method, and a die coating method. , Metering bar coating method, chamber doctor combined coating method, curtain coating method and the like.

After coating the coating liquid (b) on the base material 1, the liquid medium of the coating liquid (b) is removed by drying to form the layer (B) 3 on the base material 1.
The drying method is not particularly limited, and examples thereof include a hot air drying method, a hot roll contact method, an infrared heating method, and a microwave heating method. These methods may be performed alone or in combination. The drying temperature is not particularly limited, but when the liquid medium is the above-mentioned water or a mixed solvent of water and an organic solvent, it is usually preferably 50 to 160 ° C. Drying is usually preferably carried out under normal pressure or reduced pressure, and from the viewpoint of convenience of equipment, it is preferably carried out under normal pressure.

When the coating liquid (b) contains the silicon-containing compound (i), the drying is completed (or the drying is completed) for the purpose of increasing the proportion of the condensate in the silicon-containing compound (i) contained in the layer (B) 3. , Almost finished), the heat treatment may be performed.
The heat treatment is usually carried out at a temperature of 120 to 240 ° C., preferably 150 to 230 ° C., usually for 10 seconds to 30 minutes, preferably 20 seconds to 20 minutes.
The drying and heat treatment have some overlapping conditions such as temperature, but these do not need to be clearly distinguished and may be continuously performed.

(Step (α2))
The method for forming the layer (A) 4 is not particularly limited, and examples thereof include a method in which the coating liquid (a) is applied onto the substrate and dried.

The coating method of the coating liquid (a) is not particularly limited, and for example, a casting method, a dipping method, a roll coating method, a gravure coating method, a screen printing method, a reverse coating method, a spray coating method, a kit coating method, and a die coating method. , Metering bar coating method, chamber doctor combined coating method, curtain coating method and the like.

After applying the coating liquid (a) on the layer (B) 3, the liquid medium of the coating liquid (a) is removed by drying to form the layer (A) 4 on the layer (B) 3. .. As a result, the gas barrier layer 2 having the layer (A) 4 and the layer (B) 3 is formed.
The drying method is not particularly limited, and examples thereof include a hot air drying method, a hot roll contact method, an infrared heating method, and a microwave heating method. These methods may be performed alone or in combination. The drying temperature is not particularly limited, but when the liquid medium is an organic solvent, it is usually preferably 50 to 160 ° C. When the liquid medium is the above-mentioned water or a mixed solvent of water and an organic solvent, the temperature is usually preferably 50 to 160 ° C. Drying is usually preferably carried out under normal pressure or reduced pressure, and from the viewpoint of convenience of equipment, it is preferably carried out under normal pressure.

<Effect>
In the thermoforming gas barrier laminate 10, the gas barrier layer 2 on the base material 1 contains zinc oxide ultrafine particles, a polyester resin, and a vinyl acetate unit-containing resin, and contains zinc oxide ultrafine particles. 20 to 90% by mass with respect to the solid content, and the content of the vinyl acetate unit-containing resin is 1 to 40 parts by mass with respect to 100 parts by mass of the zinc oxide ultrafine particles, and the polycarboxylic acid. Since it has a layer (B) 3 containing an acid-based polymer, it is excellent in thermoformability. Therefore, the molded body obtained by thermoforming the thermoforming gas-barrier laminate 10 into a container shape or the like is suppressed from being lowered in gas barrier property due to thermoforming, and has excellent gas barrier property.
The reason why the above effect is exhibited is that the coating liquid forming the layer (B) contains a vinyl acetate unit-containing resin as a dispersant for the zinc oxide ultrafine particles, so that the dispersibility is good, and as a result, as described above, the layer ( It is considered that the zinc oxide ultrafine particles in B) are uniformly distributed as small particles.

<< Second Embodiment >>
FIG. 2 is a cross-sectional view schematically showing a gas barrier laminate 20 for thermoforming according to the first embodiment of the present invention. In the embodiments shown below, the above-mentioned components are designated by the same reference numerals and detailed description thereof will be omitted.
The thermoforming gas barrier laminate 20 includes a base material 1, an anchor coat layer 5 provided on the base material 1, and a gas barrier layer 2 provided on the anchor coat layer 5.
The thermoforming gas barrier laminate 20 is the same as the thermoforming gas barrier laminate 10 of the first embodiment except that the anchor coat layer 5 is provided between the base material 1 and the gas barrier layer 2. is there.

<Anchor coat layer>
The anchor coat layer 5 is a layer for increasing the interlayer adhesion strength between the base material 1 and the gas barrier layer 2.
Examples of the material constituting the anchor coat layer 5 include alkyd resin, melamine resin, acrylic resin, nitrified cotton, polyurethane resin, polyester resin, phenol resin, amino resin, fluororesin, epoxy resin, and carbodiimide group-containing resin. Resin is mentioned. Among these, polyurethane resin, polyester resin, acrylic resin, epoxy resin, carbodiimide group-containing resin and the like are preferable. These resins may be used alone or in combination of two or more.

The anchor coat layer 5 preferably contains a polyurethane resin among the resins.
As the polyol constituting the polyurethane resin, a polyester-based polyol is preferable. That is, among the polyurethane resins, polyester-based polyurethane resins are preferable. Examples of the polyester-based polyol include a reaction product of a polyvalent carboxylic acid or the like and glycols.
Examples of the polyisocyanate constituting the polyurethane resin include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, and xylyl. Examples thereof include range isocyanate and isophorone diisocyanate.
The anchor coat layer 5 may contain a carbodiimide group-containing resin from the viewpoint of adhesion to the layer (B) 3.

In the anchor coat layer 5, additives such as a curing agent and a silane coupling agent may be added to the resin, if necessary. Examples of the silane coupling agent include those similar to those mentioned in the silicon-containing compound (i) described later.

The thickness of the anchor coat layer 5 (thickness of the gas barrier laminate 20 for thermoforming before thermoforming) is not particularly limited, but is preferably in the range of 0.01 to 5 μm, preferably 0.03 to 3 μm. It is more preferably in the range of 0.05 to 2 μm, and particularly preferably in the range of 0.05 to 2 μm. If the thickness of the anchor coat layer 5 is less than the lower limit of the above range, the interlayer adhesion strength tends to be insufficient, while if it exceeds the upper limit of the above range, the desired gas barrier property tends not to be exhibited.

<Use>
The use of the thermoforming gas barrier laminate 20 is the same as that of the thermoforming gas barrier laminate 10.

<Manufacturing method of gas barrier laminate for thermoforming of the second embodiment>
Examples of the method for producing the thermoforming gas barrier laminate 20 include a production method including the following steps (β1), (β2) and (β3).
(Β1): A step of forming the anchor coat layer 5 on one surface of the base material 1.
(Β2): A step of forming the layer (B) 3 on the surface of the base material 1 on the side on which the anchor coat layer 5 is formed.
(Β3): A step of forming the layer (A) 4 on the surface of the base material 1 on the side on which the anchor coat layer 5 and the layer (B) 3 are formed.

(Step (β1))
The method for forming the anchor coat layer 5 is not particularly limited, and a known method can be appropriately selected. For example, an anchor coat layer can be formed by applying an anchor coat agent and drying it.
Examples of the anchor coating agent used for forming the anchor coating layer include those containing the above-mentioned resin or a precursor thereof, a solvent, and if necessary, an additive. As the resin or its precursor, a polyurethane-based, polyester-based or acrylic-based polymer material is preferable, and among them, a two-component consisting of a main agent containing a polyester-based polyol, which is a polyurethane-based polymer material, and a curing agent containing an isocyanate. Mold anchor coating agents are preferred.
The coating and drying of the anchor coating agent can be carried out in the same manner as the coating and drying of the coating liquid (a) in the above-mentioned step (α2).

(Step (β2))
The step (β2) can be performed in the same manner as the above-mentioned step (α1).

(Step (β3))
The step (β3) can be performed in the same manner as the above-mentioned step (α2).

<Effect>
In the thermoforming gas barrier laminate 20, the gas barrier layer 2 on the base material 1 has the layer (A) 4 and the layer (B) 3, as in the thermoforming gas barrier laminate 10. Excellent thermoformability. Further, by having the anchor coat layer 5, the interlayer adhesion strength between the base material 1 and the gas barrier layer 2 can be increased, so that the thermoformability is further excellent.

<< Third Embodiment >>
FIG. 3 is a cross-sectional view schematically showing the gas barrier laminate 30 for thermoforming according to the third embodiment of the present invention.
The thermoforming gas barrier laminate 30 includes a base material 1, an anchor coat layer 5 provided on the base material 1, a gas barrier layer 2 provided on the anchor coat layer 5, and an adhesive layer on the gas barrier layer 2. It is provided with a sealant layer 7 provided via 6.
The thermoforming gas barrier laminate 30 is the same as the thermoforming gas barrier laminate 20 of the second embodiment except that the adhesive layer 6 and the sealant layer 7 are further provided.
The sealant layer 7 may be provided directly on the gas barrier layer 2.

<Sealant layer>
The sealant layer 7 is provided on the surface of the gas barrier layer 2 according to the purpose of imparting abrasion resistance, glossiness, heat sealability, strength, moisture resistance, etc. to the thermoforming gas barrier laminate 30. It is a layer to be.

The sealant layer 7 contains a thermoplastic resin.
The thermoplastic resin in the sealant layer 7 can be appropriately determined in consideration of heat sealability and stretch moldability, and examples thereof include polyester-based polymers, polyamide-based polymers, and polyolefin-based polymers. Specific examples of these polymers include those similar to those mentioned for the base material 1. As the thermoplastic resin of the sealant layer 7, a polypropylene polymer is preferable from the viewpoint of heat sealability, stretch moldability, and heat resistance.
As the sealant layer 7, for example, the above-mentioned thermoplastic resin film can be used. The film may be stretched or unstretched.
The sealant layer 7 may be composed of a single layer or may be composed of a plurality of layers.

The thickness of the sealant layer 7 (thickness of the gas barrier laminate 30 for thermoforming before thermoforming) is appropriately determined depending on the thickness of the molded product and the like, but is preferably 1 to 2000 μm, and is preferably 10 to 10 μm. It is more preferably 1500 μm. When the thickness of the sealant layer 7 is not more than the upper limit of the above range, the gas barrier property is good. When the thickness of the sealant layer 7 is at least the lower limit of the above range, molding defects such as pinholes are unlikely to occur during thermoforming, and the thermoforming property is good.

<Adhesive layer>
The adhesive layer 6 is a layer that adheres the gas barrier layer 2 and the sealant layer 7.
The adhesive forming the adhesive layer 6 is not particularly limited, and for example, known adhesives such as acrylic, polyester, ethylene-vinyl acetate, polyurethane, vinyl chloride / vinyl acetate, and chlorinated polypropylene. Can be used.

<Use>
The use of the thermoforming gas barrier laminate 30 is the same as that of the thermoforming gas barrier laminate 10.

<Manufacturing method of gas barrier laminate for thermoforming of the third embodiment>
Examples of the method for producing the thermoforming gas barrier laminate 30 include a production method including the following steps (γ1), (γ2), (γ3) and (γ4).
(Γ1): A step of forming the anchor coat layer 5 on one surface of the base material 1.
(Γ2): A step of forming the layer (B) 3 on the surface of the base material 1 on the side on which the anchor coat layer 5 is formed.
(Γ3): A step of forming the layer (A) 4 on the surface of the base material 1 on the side on which the anchor coat layer 5 and the layer (B) 3 are formed.
(Γ4): A thermoplastic resin film (sealant layer 7) is laminated on the surface (laminated surface) on the side where the anchor coat layer 5, the layer (B) 3 and the layer (A) 4 of the base material 1 are formed. Process.

The steps (γ1), (γ2), and (γ3) are the same as those of the steps (β1), (β2), and (β3), respectively.

(Step (γ1))
The step (γ1) can be performed in the same manner as the above-mentioned step (β1).

(Step (γ2))
The step (γ2) can be performed in the same manner as the above-mentioned step (β2).
When the coating liquid (b) used in the step (γ2) contains the silicon-containing compound (i), heat treatment is performed for the purpose of increasing the proportion of the condensate in the silicon-containing compound (i) contained in the layer (B) 3. When the above is performed, the heat treatment may be performed at the time when the drying is completed (or almost completed) as described above, or at the time when the aging treatment described later is completed.

(Step (γ3))
The step (γ3) can be performed in the same manner as the above-mentioned step (β3).

(Step (γ4))
The method for laminating the thermoplastic resin film is not particularly limited, and a known method can be appropriately used. Examples thereof include a dry laminating method, an extrusion laminating method, and a hot melt laminating method.
When laminating the thermoplastic resin film, an adhesive may be used if necessary. For example, a thermoplastic resin film can be adhered to the surface of the layer (A) 4 by a dry laminating method using an adhesive. When an adhesive is used, an adhesive layer 6 is formed between the layer (A) 4 and the thermoplastic resin film (sealant layer 7). As the adhesive, a known adhesive as described above can be used.

After laminating the thermoplastic resin film in the step (γ4), the aging treatment may be performed. Examples of the aging treatment include a treatment in which the temperature is maintained at 30 to 200 ° C., preferably 30 to 150 ° C. for 0.5 to 10 days, preferably 1 to 7 days.

<Effect>
In the thermoforming gas barrier laminate 30, the gas barrier layer 2 on the base material 1 has the layer (A) 4 and the layer (B) 3, as in the thermoforming gas barrier laminate 20. Excellent thermoformability. Further, by having the anchor coat layer 5, the interlayer adhesion strength between the base material 1 and the gas barrier layer 2 can be increased, so that the thermoformability is further excellent.
Further, in the thermoforming gas barrier laminate 30, the sealant layer 7 can impart wear resistance, glossiness, heat sealability, strength, moisture resistance and the like. For example, when the surface of the gas barrier laminate 30 for thermoforming on the sealant layer 7 side is thermoformed so as to be the sealing surface of the molding container, the contents are contained in the molding container and then the lid material or the like is used. The opening can be sealed with, which is useful as a packaging material.

Although the gas barrier laminate for thermoforming of the present invention has been described above with reference to embodiments, the present invention is not limited to the above embodiments. Each configuration in the above embodiment and a combination thereof are examples, and the configuration can be added, omitted, replaced, and other changes can be made without departing from the spirit of the present invention.
For example, the layer structure of the gas barrier layer in the thermoforming gas barrier laminate of the present invention is the layer (B) and the layer in order from the base material 1 side, such as the gas barrier layer 2 shown in the first to third embodiments. It is not limited to the one in which (A) is laminated (layer (B) / layer (A)). In addition to layer (B) / layer (A), layer (A) / layer (B), layer (A) / layer (B) / layer (A), layer (B) / layer (A) / layer (B) ) Or the like.

In the gas barrier layer, the layer (A) and the layer (B) do not have to be adjacent to each other. The layer (A) and the layer (A) and the layer (in that they can easily form an ionic bond between the zinc ion derived from the zinc oxide ultrafine particles contained in the layer (A) and the carboxy group of the polycarboxylic acid polymer contained in the layer (B). It is preferable to include at least one layer constituent unit adjacent to B). A layer structure including at least one layer structure unit in which the layer (A), the layer (B), and the layer (A) are adjacent to each other, or a layer structure unit in which the layer (B), the layer (A), and the layer (B) are adjacent to each other preferable.

The thermoforming gas barrier laminate of the present invention further has a gas barrier layer having layers (A) and layers (B), an anchor coat layer, a sealant layer, and other layers other than an adhesive layer on the base material. You may.

[Molded product]
The molded product of the present invention will be described with reference to embodiments.

<< Fourth Embodiment >>
FIG. 4 is a top view showing a molded container 11 (molded article) according to a fourth embodiment of the present invention, and FIG. 5 is a VV cross-sectional view of the molded container 11.
The molded container 11 of the present embodiment is composed of a container body 12 having a round top view.

The container body 12 has a circular bottom portion 12a, a peripheral wall portion 12b rising from the peripheral edge of the bottom portion 12a, and a flange portion 12c extending substantially horizontally from the outer peripheral surface of the upper edge of the peripheral wall portion 12b. The peripheral wall portion 12b is formed in an inverted truncated cone shape in which the outer diameter gradually increases toward the upper edge.

In the container body 12, an opening is formed by the upper edge of the peripheral wall portion 12b, and the area surrounded by the bottom portion 12a and the peripheral wall portion 12b serves as a storage portion for accommodating the contents.
The diameter W of the opening of the container body 12 is not particularly limited, but may be, for example, 20 to 300 mm.
The depth D of the accommodating portion of the container body 12 is not particularly limited, but may be, for example, 20 to 100 mm.

The container body 12 uses the thermoforming gas barrier laminate 30. That is, it is composed of the thermoformed gas barrier laminate 30 for thermoforming.
In the container body 12, the thermoforming gas barrier laminate 30 is arranged so that the base material 1 side faces the outside of the container body 12 and the sealant layer 7 side faces the inside of the container body 12. Therefore, the upper surface of the flange portion 12c is composed of the sealant layer 7. As a result, after the contents are stored in the accommodating portion, the opening can be covered with a lid material or the like and heat-sealed to seal the opening.

<Manufacturing method of molded container of the fourth embodiment>
The molding container 11 (container body 12) can be manufactured by thermoforming the thermoforming gas barrier laminate 30.
As a method for producing the molded container 11, a manufacturing method including a step of heating the thermoforming gas barrier laminate 30 and stretching and molding it into a container shape to obtain a container body 12 is preferable.

Thermoforming can be performed by a known method.
As an example of the thermoforming method of the thermoforming gas barrier laminate 30, there is a method of vacuum forming the thermoforming gas barrier laminate 30 by heating and softening it using a vacuum forming machine. Specifically, the thermoforming gas barrier laminate 30 is heated and softened for about 5 to 30 seconds in a heating furnace set at 400 to 500 ° C. The temperature of the thermoforming gas barrier laminate 30 can be adjusted by the heating temperature and the heating time at this time. Immediately after heating, the thermoforming gas barrier laminate 30 is placed on a molding mold (resin mold or metal mold) having an arbitrary shape, and the air between the thermoforming gas barrier laminate 30 and the molding mold is sucked. The thermoforming gas barrier laminate 30 is brought into close contact with the molding die, cooled, and molded into a mold shape.
However, the stretch molding method is not limited to this. The molding machine is not limited to the vacuum forming machine, and a compressed air molding machine, a melt molding machine, or the like may be used. Further, if necessary, a known molding method such as a method of further molding into a mold shape using a plug (straight method, drape method, air slip method, snapback method, plug assist method) can be used.

The molded container 11 (container body 12) obtained as described above can be heat-sterilized. By performing heat sterilization treatment, zinc ions derived from the zinc oxide ultrafine particles in layer (A) 4 are transferred to layer (B) 3, and the zinc ions and the carboxy group of the polycarboxylic acid-based polymer are combined. An ionic bond can be formed between them. Thereby, excellent gas barrier property can be exhibited.

Heat sterilization treatment refers to treatment in an atmosphere of high temperature and high humidity or exposure to hot water. Specific examples of such heat sterilization treatment include boil treatment, retort treatment, sterilization treatment used for aseptic packaged rice and the like.
The treatment temperature of the heat sterilization treatment is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, from the viewpoint of gas barrier properties.
Further, when the heat sterilization treatment is a treatment for exposing the molded container to a high temperature and high humidity atmosphere, the relative humidity of the atmosphere is preferably 90% or more.

The heat sterilization treatment may be performed before the contents are contained in the molding container 11, or may be performed after the contents are contained and the opening is sealed with a lid material if necessary. When performed after accommodating the contents, the heat sterilization treatment can also serve as the heat sterilization treatment of the contents.
Specific examples of contents that require heat sterilization include seasoned foods (curry, stew, etc.), cooked foods for microwave ovens (baby food, cooked rice, lady meal, etc.), soups, desserts, pets, etc. Examples include foods (especially wet types) and processed agricultural and livestock products.
The molded container 11 can be suitably used as a packaging container for foods as mentioned in the above example.
The lid material preferably has a sealant layer on the surface (sealing surface) in contact with the molding container 11, and the sealant layer contains a thermoplastic resin of the same type as the thermoplastic resin of the sealant layer 7 of the molding container 11. .. For example, if the thermoplastic resin of the sealant layer 7 of the molding container 11 is a polypropylene-based polymer, it is preferable that the thermoplastic resin of the sealant layer of the lid material is also a polypropylene-based polymer. The shape of the lid material is not particularly limited, and may be a sheet shape or a three-dimensional shape.

Although the molded product of the present invention has been described above with reference to embodiments, the present invention is not limited to the above-described embodiments. Each configuration in the above embodiment and a combination thereof are examples, and the configuration can be added, omitted, replaced, and other changes can be made without departing from the spirit of the present invention.
For example, the molded article of the present invention is not limited to the molded container shown in the fourth embodiment. For example, the shape of the container body of the molded container when viewed from above may be a shape other than the round shape as described above, for example, a polygonal shape such as a square shape. Further, the cross-sectional shape may be a line-symmetrical shape as described above or an asymmetrical shape. Further, the molding container may be in the form of a single container (container body 12) such as the molding container 11, or in a form in which two or more containers are connected. When two or more containers are connected, the shape and size of each container may be the same or different.
The molded product of the present invention may be a molded product other than a molded container. Examples of molded products other than molded containers include bags such as pouches. A spout may be attached to the bag.

Hereinafter, the present invention will be specifically described based on Examples and Comparative Examples. However, the present invention is not limited to the following examples.
The materials used in Preparation Examples 1 to 13 are shown below.

<Material used>
Zinc oxide ultrafine particles: FINEX50 manufactured by Sakai Chemical Industry Co., Ltd., average primary particle size 20 nm.
Vinyl acetate unit-containing resin (1): Saknol SN-12T (monopolymer of vinyl acetate) manufactured by Denka Co., Ltd., solid content concentration 20% by mass (diluted solvent: ethyl acetate).
Vinyl acetate unit-containing resin (2): SOLBIN C (vinyl chloride / vinyl acetate copolymer resin) manufactured by Nisshin Kagaku Kogyo Co., Ltd., solid content concentration 20% by mass (diluted solvent: ethyl acetate).
Vinyl acetate unit-containing resin (3): M1008 (vinyl chloride / vinyl acetate copolymer resin) manufactured by Kaneka Co., Ltd., solid content concentration 20% by mass (diluted solvent: ethyl acetate).
Sodium polycarboxylic acid (4): Poise 521 manufactured by Kao Corporation, solid content concentration 40% by mass, average molecular weight 20,000 (diluted solvent: water).
Polyester resin (5): Unitika Ltd. Elitel UE-3220, solid content concentration 20% by mass (diluted solvent: ethyl acetate).
Polyester resin (6): Takelac A525 manufactured by Mitsui Chemicals, Inc., solid content concentration 50% by mass (diluted solvent: ethyl acetate).
Polyester resin (7): Elitel KT-8803 manufactured by Unitica Co., Ltd., solid content concentration 30% by mass (aqueous dispersion of polyester resin, number average molecular weight of polyester resin 13,000, glass transition temperature 65 ° C, acid value 7 mgKOH / g).

<Preparation of coating liquid>
(Preparation Example 1)
To 60 g of ethyl acetate, 20 g of ultrafine zinc oxide fine particles and 20 g of vinyl acetate unit-containing resin (1) as a dispersant are added, and after sufficiently stirring with a stirrer, 30.0 g of this is a planetary ball mill (P- of Fritsch). After sufficiently dispersing the zirconia beads having a diameter of 0.3 mm in 7), the zirconia beads were separated by a sieve to obtain a zinc oxide ultrafine particle dispersion. To 3.0 g of this zinc oxide ultrafine particle dispersion, 5.6 g of ethyl acetate and 11.4 g of polyester resin (5) are added and stirred to obtain a coating liquid (a-1) (solid content concentration: 15% by mass). It was.

(Preparation Example 2)
To 60 g of ethyl acetate, 20 g of ultrafine zinc oxide fine particles and 20 g of vinyl acetate unit-containing resin (1) as a dispersant are added, and after sufficiently stirring with a stirrer, 30.0 g of this is a planetary ball mill (P- of Fritsch). After sufficiently dispersing the zirconia beads having a diameter of 0.3 mm in 7), the zirconia beads were separated by a sieve to obtain a zinc oxide ultrafine particle dispersion. To 9.0 g of this zinc oxide ultrafine particle dispersion liquid, 6.8 g of ethyl acetate and 4.2 g of polyester resin (5) are added and stirred to obtain a coating liquid (a-2) (solid content concentration: 15% by mass). It was.

(Preparation Example 3)
To 77 g of ethyl acetate, 20 g of ultrafine zinc oxide particles and 3.0 g of vinyl acetate unit-containing resin (1) as a dispersant are added, and after sufficiently stirring with a stirrer, 30.0 g of this is a planetary ball mill (manufactured by Fritsch). After sufficiently dispersing with zirconia beads having a diameter of 0.3 mm in P-7), the zirconia beads were separated by a sieve to obtain a zinc oxide ultrafine particle dispersion. To 13.5 g of this zinc oxide ultrafine particle dispersion liquid, 6.1 g of ethyl acetate and 0.42 g of polyester resin (5) are added and stirred to obtain a coating liquid (a-3) (solid content concentration: 15% by mass). It was.

(Preparation Example 4)
To 79 g of ethyl acetate, 20 g of ultrafine zinc oxide particles and 1.0 g of vinyl acetate unit-containing resin (1) as a dispersant are added, and after sufficiently stirring with a stirrer, 30.0 g of this is a planetary ball mill (manufactured by Fritsch). After sufficiently dispersing with zirconia beads having a diameter of 0.3 mm in P-7), the zirconia beads were separated by a sieve to obtain a zinc oxide ultrafine particle dispersion. To 9.0 g of this zinc oxide ultrafine particle dispersion liquid, 5.1 g of ethyl acetate and 5.9 g of polyester resin (5) are added and stirred to obtain a coating liquid (a-4) (solid content concentration: 15% by mass). It was.

(Preparation Example 5)
To 45 g of ethyl acetate, 20 g of ultrafine zinc oxide particles and 35 g of vinyl acetate unit-containing resin (1) as a dispersant are added, and the mixture is sufficiently stirred with a stirrer. After sufficiently dispersing the zirconia beads having a diameter of 0.3 mm in 7), the zirconia beads were separated by a sieve to obtain a zinc oxide ultrafine particle dispersion. To 9.0 g of this zinc oxide ultrafine particle dispersion liquid, 8.15 g of ethyl acetate and 2.85 g of polyester resin (5) are added and stirred to obtain a coating liquid (a-5) (solid content concentration: 15% by mass). It was.

(Preparation Example 6)
To 60 g of ethyl acetate, 20 g of ultrafine zinc oxide fine particles and 20 g of vinyl acetate unit-containing resin (2) as a dispersant are added, and after sufficiently stirring with a stirrer, 30.0 g of this is a planetary ball mill (P- of Fritsch). After sufficiently dispersing the zirconia beads having a diameter of 0.3 mm in 7), the zirconia beads were separated by a sieve to obtain a zinc oxide ultrafine particle dispersion. To 3.0 g of this zinc oxide ultrafine particle dispersion, 5.6 g of ethyl acetate and 11.4 g of polyester resin (5) are added and stirred to obtain a coating liquid (a-6) (solid content concentration: 15% by mass). It was.

(Preparation Example 7)
To 60 g of ethyl acetate, 20 g of ultrafine zinc oxide fine particles and 20 g of vinyl acetate unit-containing resin (2) as a dispersant are added, and after sufficiently stirring with a stirrer, 30.0 g of this is a planetary ball mill (P- of Fritsch). After sufficiently dispersing the zirconia beads having a diameter of 0.3 mm in 7), the zirconia beads were separated by a sieve to obtain a zinc oxide ultrafine particle dispersion. To 9.0 g of this zinc oxide ultrafine particle dispersion liquid, 6.8 g of ethyl acetate and 4.2 g of polyester resin (5) are added and stirred to obtain a coating liquid (a-7) (solid content concentration: 15% by mass). It was.

(Preparation Example 8)
To 77 g of ethyl acetate, 20 g of ultrafine zinc oxide particles and 3.0 g of vinyl acetate unit-containing resin (2) as a dispersant are added, and after sufficiently stirring with a stirrer, 30.0 g of this is a planetary ball mill (manufactured by Fritsch). After sufficiently dispersing with zirconia beads having a diameter of 0.3 mm in P-7), the zirconia beads were separated by a sieve to obtain a zinc oxide ultrafine particle dispersion. To 13.5 g of this zinc oxide ultrafine particle dispersion liquid, 6.1 g of ethyl acetate and 0.42 g of polyester resin (5) are added and stirred to obtain a coating liquid (a-8) (solid content concentration: 15% by mass). It was.

(Preparation Example 9)
To 79 g of ethyl acetate, 20 g of ultrafine zinc oxide particles and 1.0 g of vinyl acetate unit-containing resin (2) as a dispersant are added, and after sufficiently stirring with a stirrer, 30.0 g of this is a planetary ball mill (manufactured by Fritsch). After sufficiently dispersing with zirconia beads having a diameter of 0.3 mm in P-7), the zirconia beads were separated by a sieve to obtain a zinc oxide ultrafine particle dispersion. To 9.0 g of this zinc oxide ultrafine particle dispersion liquid, 5.1 g of ethyl acetate and 5.9 g of polyester resin (5) are added and stirred to obtain a coating liquid (a-9) (solid content concentration: 15% by mass). It was.

(Preparation Example 10)
To 45 g of ethyl acetate, 20 g of ultrafine zinc oxide particles and 35 g of vinyl acetate unit-containing resin (2) as a dispersant are added, and the mixture is sufficiently stirred with a stirrer. After sufficiently dispersing the zirconia beads having a diameter of 0.3 mm in 7), the zirconia beads were separated by a sieve to obtain a zinc oxide ultrafine particle dispersion. To 9.0 g of this zinc oxide ultrafine particle dispersion liquid, 8.15 g of ethyl acetate and 2.85 g of polyester resin (5) are added and stirred to obtain a coating liquid (a-10) (solid content concentration: 15% by mass). It was.

(Preparation Example 11)
To 60 g of ethyl acetate, 20 g of ultrafine zinc oxide particles and 20 g of vinyl acetate unit-containing resin (3) as a dispersant are added, and the mixture is sufficiently stirred with a stirrer. After sufficiently dispersing the zirconia beads having a diameter of 0.3 mm in 7), the zirconia beads were separated by a sieve to obtain a zinc oxide ultrafine particle dispersion. To 9.0 g of this zinc oxide ultrafine particle dispersion liquid, 6.8 g of ethyl acetate and 4.2 g of polyester resin (5) are added and stirred to obtain a coating liquid (a-11) (solid content concentration: 15% by mass). It was.

(Preparation Example 12)
To 60 g of ethyl acetate, 20 g of ultrafine zinc oxide fine particles and 20 g of vinyl acetate unit-containing resin (1) as a dispersant are added, and after sufficiently stirring with a stirrer, 30.0 g of this is a planetary ball mill (P- of Fritsch). After sufficiently dispersing the zirconia beads having a diameter of 0.3 mm in 7), the zirconia beads were separated by a sieve to obtain a zinc oxide ultrafine particle dispersion. To 9.0 g of this zinc oxide ultrafine particle dispersion liquid, 9.3 g of ethyl acetate and 1.7 g of polyester resin (6) are added and stirred to obtain a coating liquid (a-12) (solid content concentration: 15% by mass). It was.

(Preparation Example 13)
To 60 g of ethyl acetate, 20 g of ultrafine zinc oxide fine particles and 20 g of vinyl acetate unit-containing resin (2) as a dispersant are added, and after sufficiently stirring with a stirrer, 30.0 g of this is a planetary ball mill (P- of Fritsch). After sufficiently dispersing the zirconia beads having a diameter of 0.3 mm in 7), the zirconia beads were separated by a sieve to obtain a zinc oxide ultrafine particle dispersion. To 9.0 g of this zinc oxide ultrafine particle dispersion liquid, 9.3 g of ethyl acetate and 1.7 g of polyester resin (6) are added and stirred to obtain a coating liquid (a-13) (solid content concentration: 15% by mass). It was.

(Preparation Example 14)
To 60 g of ethyl acetate, 20 g of ultrafine zinc oxide fine particles and 20 g of vinyl acetate unit-containing resin (1) as a dispersant are added, and after sufficiently stirring with a stirrer, 30.0 g of this is a planetary ball mill (P- of Fritsch). After sufficiently dispersing the zirconia beads having a diameter of 0.3 mm in 7), the zirconia beads were separated by a sieve to obtain a zinc oxide ultrafine particle dispersion. To 0.75 g of this zinc oxide ultrafine particle dispersion liquid, 5.2 g of ethyl acetate and 14.1 g of polyester resin (5) are added and stirred to obtain a coating liquid (a-14) (solid content concentration: 15% by mass). It was.

(Preparation Example 15)
To 77 g of ethyl acetate, 20 g of ultrafine zinc oxide particles and 3 g of vinyl acetate unit-containing resin (1) as a dispersant are added, and the mixture is sufficiently stirred with a stirrer. After sufficiently dispersing the zirconia beads having a diameter of 0.3 mm in 7), the zirconia beads were separated by a sieve to obtain a zinc oxide ultrafine particle dispersion. To 14.3 g of this zinc oxide ultrafine particle dispersion liquid, 5.4 g of ethyl acetate and 0.32 g of polyester resin (5) are added and stirred to obtain a coating liquid (a-15) (solid content concentration: 15% by mass). It was.

(Preparation Example 16)
20 g of zinc oxide ultrafine particles are added to 80 g of ethyl acetate, and the mixture is sufficiently stirred with a stirrer, and then 30.0 g of this is sufficiently used with a planetary ball mill (P-7 manufactured by Fritsch) using zirconia beads having a diameter of 0.3 mm. The zirconia beads were separated by sieving to obtain a zinc oxide ultrafine particle dispersion. To 9.0 g of this zinc oxide ultrafine particle dispersion liquid, 5.0 g of ethyl acetate and 6.0 g of polyester resin (5) are added and stirred to obtain a coating liquid (a-16) (solid content concentration: 15% by mass). It was.

(Preparation Example 17)
To 79.5 g of ethyl acetate, 20 g of ultrafine zinc oxide particles and 0.5 g of vinyl acetate unit-containing resin (1) as a dispersant are added, and the mixture is sufficiently stirred with a stirrer. After sufficiently dispersing the zirconia beads having a diameter of 0.3 mm with P-7) manufactured by the same company, the zirconia beads were separated by a sieve to obtain a zinc oxide ultrafine particle dispersion. To 9.0 g of this zinc oxide ultrafine particle dispersion liquid, 5.05 g of ethyl acetate and 5.96 g of polyester resin (5) are added and stirred to obtain a coating liquid (a-17) (solid content concentration: 15% by mass). It was.

(Preparation Example 18)
To 30 g of ethyl acetate, 20 g of ultrafine zinc oxide particles and 50 g of vinyl acetate unit-containing resin (1) as a dispersant are added, and the mixture is sufficiently stirred with a stirrer. After sufficiently dispersing the zirconia beads having a diameter of 0.3 mm in 7), the zirconia beads were separated by a sieve to obtain a zinc oxide ultrafine particle dispersion. To 9.0 g of this zinc oxide ultrafine particle dispersion liquid, 9.5 g of ethyl acetate and 1.5 g of polyester resin (5) are added and stirred to obtain a coating liquid (a-18) (solid content concentration: 15% by mass). It was.

(Preparation Example 19)
To 66.3 g of distilled water, 30.0 g of ultrafine zinc oxide fine particles and 3.75 g of sodium polycarboxylic acid (4) as a dispersant were added, and the mixture was sufficiently stirred with a stirrer. After sufficiently dispersing the zirconia beads having a diameter of 0.3 mm with P-7) manufactured by Fritsch, the zirconia beads were separated by sieving to obtain a zinc oxide ultrafine water dispersion. To 6.0 g of this zinc oxide ultrafine water dispersion liquid, 6.9 g of distilled water and 3.7 g of polyester resin (7) are added and stirred, and then 3.4 g of isopropyl alcohol is added and stirred, and the coating liquid (a) is added. -19) (solid content concentration 15% by mass) was obtained.

(Preparation Example 20)
Polyacrylic acid (trade name: Aron A-10H, number average molecular weight 200,000, solid content concentration 25% by mass aqueous solution, manufactured by Toagosei Co., Ltd.) and glycerin are 90/10 by mass ratio (solid content ratio). The coating liquid (b-1) was prepared by adding 2.55 parts by mass of 3-glycidoxypropyltrimethoxysilane to 100 parts by mass of polyacrylic acid.

<Manufacturing of gas barrier laminate for thermoforming>
(Example 1)
Polyester-based main agent (Mitsui Chemical Polyurethane Co., Ltd., Takelac (registered trademark) A525: solid content concentration 50 parts by mass) and curing agent (Mitsui Chemical Polyurethane Co., Ltd., Takenate (registered trademark) A52: solid content concentration 75 parts by mass) Was dissolved in a solvent (ethyl acetate) so that the mass ratio (main agent / curing agent) was 9/1 to obtain a coating liquid for an anchor coat layer having a solid content concentration of 5 parts by mass.
The obtained coating liquid for the anchor coat layer is applied onto an unstretched polyester film (thickness 25 μm) using a bar coater so that the thickness after drying is 1.0 μm, and dried with a dryer. An anchor coat layer was formed.
The coating liquid (b-1) was applied onto the formed anchor coat layer using a bar coater so as to have a thickness of 1.0 μm after drying, and dried to form a layer.
Next, the coating liquid (a-1) is coated and dried on the layer formed from the coating liquid (b-1) using the bar coater so that the thickness after drying is 1.2 μm. To form a layer.
In this way, the anchor coat layer, the layer formed from the coating liquid (b-1) (layer (B)), and the layer formed from the coating liquid (a-1) (layer (A)) on the polyester film. However, a gas barrier laminate for thermoforming was obtained, which was laminated in this order.

(Example 2)
A gas barrier laminate for thermoforming was obtained in the same manner as in Example 1 except that the coating liquid (a-2) was used instead of the coating liquid (a-1).

(Example 3)
A gas barrier laminate for thermoforming was obtained in the same manner as in Example 1 except that the coating liquid (a-3) was used instead of the coating liquid (a-1).

(Example 4)
A gas barrier laminate for thermoforming was obtained in the same manner as in Example 1 except that the coating liquid (a-4) was used instead of the coating liquid (a-1).

(Example 5)
A gas barrier laminate for thermoforming was obtained in the same manner as in Example 1 except that the coating liquid (a-5) was used instead of the coating liquid (a-1).

(Example 6)
A gas barrier laminate for thermoforming was obtained in the same manner as in Example 1 except that the coating liquid (a-6) was used instead of the coating liquid (a-1).

(Example 7)
A gas barrier laminate for thermoforming was obtained in the same manner as in Example 1 except that the coating liquid (a-7) was used instead of the coating liquid (a-1).

(Example 8)
A gas barrier laminate for thermoforming was obtained in the same manner as in Example 1 except that the coating liquid (a-8) was used instead of the coating liquid (a-1).

(Example 9)
A gas barrier laminate for thermoforming was obtained in the same manner as in Example 1 except that the coating liquid (a-9) was used instead of the coating liquid (a-1).

(Example 10)
A gas barrier laminate for thermoforming was obtained in the same manner as in Example 1 except that the coating liquid (a-10) was used instead of the coating liquid (a-1).

(Example 11)
A gas barrier laminate for thermoforming was obtained in the same manner as in Example 1 except that the coating liquid (a-11) was used instead of the coating liquid (a-1).

(Example 12)
A gas barrier laminate for thermoforming was obtained in the same manner as in Example 1 except that the coating liquid (a-12) was used instead of the coating liquid (a-1).

(Example 13)
A gas barrier laminate for thermoforming was obtained in the same manner as in Example 1 except that the coating liquid (a-13) was used instead of the coating liquid (a-1).

(Comparative Example 1)
A gas barrier laminate for thermoforming was obtained in the same manner as in Example 1 except that the coating liquid (a-14) was used instead of the coating liquid (a-1).

(Comparative Example 2)
A gas barrier laminate for thermoforming was obtained in the same manner as in Example 1 except that the coating liquid (a-15) was used instead of the coating liquid (a-1).

(Comparative Example 3)
A gas barrier laminate for thermoforming was obtained in the same manner as in Example 1 except that the coating liquid (a-16) was used instead of the coating liquid (a-1).

(Comparative Example 4)
A gas barrier laminate for thermoforming was obtained in the same manner as in Example 1 except that the coating liquid (a-17) was used instead of the coating liquid (a-1).

(Comparative Example 5)
A gas barrier laminate for thermoforming was obtained in the same manner as in Example 1 except that the coating liquid (a-18) was used instead of the coating liquid (a-1).

(Comparative Example 6)
A gas barrier laminate for thermoforming was obtained in the same manner as in Example 1 except that the coating liquid (a-19) was used instead of the coating liquid (a-1).

<Evaluation 1: Thermoformability>
(1) Preparation of laminated sheet:
Using an adhesive, a small tabletop laminator manufactured by Tester Sangyo Co., Ltd. was used to combine the gas barrier laminates for thermoforming (Examples 1 to 13 and Comparative Examples 1 to 6) obtained in each example with an unstretched product having a thickness of 600 μm. By laminating with a polypropylene film (CPP), a laminated sheet having a structure of a gas barrier laminate for thermoforming / adhesive / CPP was obtained. The thermoforming gas barrier laminate was arranged so that the laminate surface (the surface on the gas barrier layer side) was in contact with the adhesive. As the adhesive, a two-component curable adhesive manufactured by Mitsui Chemicals, Inc., Takelac A525 (main agent) / Takenate A52 (curing agent) was used. The obtained laminated sheets were laminated and then cured at 40 ° C. for 3 days.

(2) Preparation of molding container (molded body) by thermoforming:
The obtained laminated sheet (composition; gas barrier laminate for thermoforming / adhesive / CPP) was used in the same manner as the molding container 11 shown in FIGS. 4 to 5 using a vacuum / compressed air molding machine manufactured by Yanagishita Giken Co., Ltd. A molded container was obtained by thermoforming into the shape of. The diameter W of the molding container was 40 mm, and the depth D was 25 mm.

(3) Measurement of oxygen permeability:
The obtained molded container was subjected to a retort treatment at a temperature of 120 ° C. for 30 minutes using a retort processing machine (Hisaka Works, Ltd .: RCS-600) as a heat sterilization treatment. The oxygen permeability of the molded container after the retort treatment was measured using an oxygen permeation tester (OXTRAN2 / 20, manufactured by Modern Control) when the temperature inside and outside the container was 20 ° C. and the relative humidity was 50%. The measured value of oxygen permeability one day after the start of measurement was converted using the values of oxygen concentration in the atmosphere (20%) and container surface area (0.018 m ² ), and JIS K-7126 "B method". (Isometric method) ”and, in accordance with ASTM D3985-81, expressed in oxygen permeability at ^{an oxygen concentration of 100% and a surface area of 1 m 2 [unit: cm 3} (STP) / (m ² · day · MPa)]. .. Here, (STP) means a standard condition (0 ° C., 1 atm) for defining the volume of oxygen. The lower the oxygen permeability of the molding container, the better the thermoforming property. The evaluation results are shown in Table 1.
In Comparative Example 6, the oxygen permeability was not measured because it could not be stretched during thermoforming and the laminated sheet was broken, and it was displayed as "x (molding impossible)" in Table 1.

<Evaluation 2: Stability of coating liquid (a)>
With respect to the coating liquids (a-1) to (a-19) used for forming the layer (A) in Examples and Comparative Examples, the presence or absence of precipitation of zinc oxide ultrafine particles was visually observed immediately after preparation, and the following criteria were used. Evaluated in. The evaluation results are shown in Table 1.
◯: No sedimentation.
×: There is sedimentation.

As is clear from the results shown in Table 1, the coating liquid used for forming the layer (A) in Examples 1 to 13 had good liquid stability.
Further, the molding container obtained by thermoforming the thermoforming gas barrier laminate obtained in Examples 1 to 13 had excellent gas barrier properties. From this, the thermoforming gas barrier laminates of Examples 1 to 13 are excellent in thermoformability, and when the thermoforming gas barrier laminate is thermoformed and heat sterilized, it has excellent gas barrier properties. It was confirmed that a molded product having the above can be obtained.

According to the present invention, it is possible to provide a gas barrier laminate for thermoforming in which the molded product obtained by thermoforming and heat sterilization has excellent gas barrier properties, and a molded product using the same.

1 base material 2 gas barrier layer 3 layers (B)
4 layers (A)
5 Anchor coat layer 6 Adhesive layer 7 Sealant layer 10, 20, 30 Gas barrier laminate for thermoforming 11 Molded container (molded product)
12 Container body

Claims (10)

A gas barrier laminate for thermoforming having a base material and a gas barrier layer formed on the base material.
The gas barrier layer has a layer (A) containing zinc oxide ultrafine particles, a polyester resin, and a vinyl acetate unit-containing resin, and a layer (B) containing a polycarboxylic acid polymer.
The content of the zinc oxide ultrafine particles is 20 to 90% by mass with respect to the total mass of the layer (A).
A gas barrier laminate for thermoforming in which the content of the vinyl acetate unit-containing resin is 1 to 40 parts by mass with respect to 100 parts by mass of the zinc oxide ultrafine particles. The layer (A) is a layer formed from a coating liquid.
The coating liquid contains zinc oxide ultrafine particles, a polyester resin, a vinyl acetate unit-containing resin, and a liquid medium.
The content of the zinc oxide ultrafine particles is 20 to 90% by mass with respect to the total mass of the total solid content in the coating liquid.
The content of vinyl acetate units containing resin, the thermoforming gas barrier laminate according to claim 1 which is 1 to 40 parts by weight with respect to zinc oxide ultrafine particles 100 parts by weight. The gas barrier laminate for thermoforming according to claim 2 , wherein the liquid medium is an organic solvent. A coating liquid that forms a layer constituting a gas barrier layer in combination with a layer containing a polycarboxylic acid-based polymer.
It contains zinc oxide ultrafine particles, a polyester resin, a vinyl acetate unit-containing resin, and a liquid medium.
The content of the zinc oxide ultrafine particles is 20 to 90% by mass with respect to the total mass of the total solid content in the coating liquid.
A coating liquid in which the content of the vinyl acetate unit-containing resin is 1 to 40 parts by mass with respect to 100 parts by mass of the zinc oxide ultrafine particles. A coating liquid that forms the layer (A) of the thermoforming gas barrier laminate according to claim 1.
It contains zinc oxide ultrafine particles, a polyester resin, a vinyl acetate unit-containing resin, and a liquid medium.
The content of the zinc oxide ultrafine particles is 20 to 90% by mass with respect to the total mass of the total solid content in the coating liquid.
A coating liquid in which the content of the vinyl acetate unit-containing resin is 1 to 40 parts by mass with respect to 100 parts by mass of the zinc oxide ultrafine particles. The coating liquid according to claim 4 or 5 , wherein the liquid medium is an organic solvent. A step of forming a layer (B) containing a polycarboxylic acid-based polymer on one surface of a base material, and a coating liquid (a) on the surface of the base material on the side on which the layer (B) is formed. Including the steps of coating and drying to form the layer (A).
The coating liquid (a) contains zinc oxide ultrafine particles, a polyester resin, a vinyl acetate unit-containing resin, and a liquid medium, and the content of the zinc oxide ultrafine particles is the content of the zinc oxide ultrafine particles in the coating liquid (a). A gas barrier for thermal molding, which is 20 to 90% by mass with respect to the total mass of the total solid content, and the content of the vinyl acetate unit-containing resin is 1 to 40 parts by mass with respect to 100 parts by mass of the zinc oxide ultrafine particles. A method for producing a sex laminate . A step of applying the coating liquid (a) on one surface of the base material and drying it to form the layer (A), and a polycarboxylic acid on the surface of the base material on the side on which the layer (A) is formed. Including a step of forming a layer (B) containing an acid-based polymer.
The coating liquid (a) contains zinc oxide ultrafine particles, a polyester resin, a vinyl acetate unit-containing resin, and a liquid medium, and the content of the zinc oxide ultrafine particles is the content of the zinc oxide ultrafine particles in the coating liquid (a). A gas barrier for thermal molding, which is 20 to 90% by mass with respect to the total mass of the total solid content, and the content of the vinyl acetate unit-containing resin is 1 to 40 parts by mass with respect to 100 parts by mass of the zinc oxide ultrafine particles. A method for producing a sex laminate . The method for producing a gas barrier laminate for thermoforming according to claim 7 or 8 , wherein the liquid medium is an organic solvent. A molded product using the gas barrier laminate for thermoforming according to claim 1 or 2.

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