JP2019019206A - Coating liquid, thermoforming gas barrier laminate and molding - Google Patents

Abstract

To provide a coating liquid capable of manufacturing a gas barrier laminate excellent in thermoforming properties, while excellent in dispersibility of zinc oxide ultrafine particles even if a liquid medium is nonaqueous.SOLUTION: A coating liquid includes an amine salt of a polyester acid based resin, a polyether phosphoric ester based resin (however, excluding an amine salt), one or more kinds of dispersant selected from fatty acid ester, zinc oxide ultrafine particles, a polyester resin (however, excluding a polyester acid based resin), and an organic solvent. A content of the zinc oxide ultrafine particles is 20-90 mass% with regard to a total mass of a total solid in the coating liquid. A content of the dispersant is 1-40 pts.mass with regard to the zinc oxide ultrafine particles of 100 pts.mass.SELECTED DRAWING: None

Description

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

There is known a gas barrier film formed by coating a coating liquid containing ultrafine particles of a polyvalent metal compound such as zinc oxide on a layer containing a polycarboxylic acid polymer. Such a gas barrier film has excellent gas barrier properties by performing heat sterilization treatment such as retort treatment and boil treatment.
Patent Document 1 proposes a coating solution containing zinc oxide ultrafine particles, a polyester resin, sodium polycarboxylate and water. This coating solution is said to have good dispersibility of zinc oxide ultrafine particles by using polycarboxylic acid sodium salt as a dispersant. A gas barrier laminate having a layer formed from this coating solution 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 solution proposed in Patent Document 1 and a layer containing a polycarboxylic acid-based polymer is thermoformed into a container shape or the like and subjected to a heat sterilization treatment. The gas barrier property is not sufficient (the thermoformability is insufficient). Therefore, this gas barrier laminate cannot be applied to a molded container or the like.
By adding a resin such as a thermoplastic resin or a thermosetting resin to the coating liquid, the gas barrier laminate having a layer formed from the coating liquid and a layer containing polyacrylic acid is given stretchability, It is conceivable to improve the moldability. However, many of these resins are non-aqueous solvent systems that do not dissolve in water but dissolve in non-aqueous solvents. When a non-aqueous solvent-based resin is blended with the above coating liquid in which zinc oxide ultrafine particles are dispersed and water is used as a liquid medium in which sodium polycarboxylate is dissolved, there is a problem in that the resin precipitates and the coating liquid The fabrication itself is difficult. Therefore, it is difficult to apply a non-aqueous solvent resin to the coating liquid.

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

  As a result of intensive studies to achieve the above object, the present inventors have been selected from among amine salts of polyester acid resins, polyether phosphate ester resins (excluding amine salts) and fatty acid esters as dispersants. By using one or more of the above, it was found that even when a non-aqueous liquid medium was used, a coating liquid having good dispersibility of zinc oxide ultrafine particles was obtained, and the present invention was completed. .

The present invention has the following aspects.
<1> Amine salt of polyester acid resin, polyether phosphate ester resin (excluding amine salt), one or more dispersants selected from fatty acid esters, zinc oxide ultrafine particles, polyester resin ( However, a polyester acid resin is excluded) and an organic solvent, and the content of the zinc oxide ultrafine particles is 20 to 90% by mass with respect to the total mass of all solids in the coating liquid, and the dispersant The coating liquid whose content is 1-40 mass parts with respect to 100 mass parts of said zinc oxide ultrafine particles.
<2> A thermoforming gas barrier laminate having a base material and a gas barrier layer formed on the base material, wherein the gas barrier layer is an amine salt of a polyester acid resin, a polyether phosphate ester type A layer (A) comprising a resin (excluding an amine salt), one or more dispersants selected from fatty acid esters, zinc oxide ultrafine particles, and a polyester-based resin (except a polyester acid-based resin); A layer (B) containing a polycarboxylic acid polymer, and 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 having a content of 1 to 40 parts by mass with respect to 100 parts by mass of the zinc oxide ultrafine particles.
<3> The gas barrier laminate for thermoforming according to <2>, wherein the layer (A) is a layer formed from the coating liquid according to <1>.
<4> A molded body using the thermoforming gas barrier laminate according to <2> or <3>.

The coating liquid of the present invention can produce a gas barrier laminate having good dispersibility of zinc oxide ultrafine particles and excellent thermoformability even when the liquid medium is non-aqueous.
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. For this reason, the molded article of the present invention using this has suppressed gas barrier properties from being lowered by thermoforming, and has excellent gas barrier properties.

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

  Hereinafter, embodiments of the coating liquid, the thermoforming gas barrier laminate and the molded body of the present invention will be described. However, this embodiment is specifically described in order to make the gist of the invention better understood, and does not limit the present invention unless otherwise specified.

≪Coating liquid≫
The coating liquid of the present invention (hereinafter also referred to as coating liquid (a)) is one kind selected from amine salts of polyester acid resins, polyether phosphate resins (excluding amine salts), and fatty acid esters. It contains the above dispersant, zinc oxide ultrafine particles, a polyester-based resin, and an organic solvent.
The coating liquid (a) may further contain other components other than the dispersant, the zinc oxide ultrafine particles, the polyester resin, and the organic solvent, if necessary.

<Dispersant>
The dispersant of the present embodiment is at least one selected from amine salts of polyester acid resins, polyether phosphate ester resins (excluding amine salts), and fatty acid esters.
When the coating liquid (a) contains the dispersant, the dispersibility of the zinc oxide ultrafine particles is further improved.
Each component contained in the dispersant may be used alone or in combination of two or more.

(Amine salt of polyester acid resin)
The amine salt of the polyester acid resin is an acid amine salt of a polycondensate (containing a carboxyl group in the side chain) of a polyvalent carboxylic acid and a polyhydric alcohol. Examples of the amine salt of the polyester acid resin include amidoamine having an amide bond in one molecule.
The number average molecular weight of the amine salt of the polyester acid resin is preferably 300,000 or less, and 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.

(Polyether phosphate ester resin (excluding amine salts))
The polyether phosphate ester resin is a polycondensate of polyvalent carboxylic acid and phosphoric acid. However, in this embodiment, amine salts are excluded. Examples of the polyether phosphate ester resin include a sodium salt of a polycondensate of dicarboxylic acid and phosphoric acid.
The number average molecular weight of the polyether phosphate ester resin (excluding the amine salt) is preferably 300,000 or less, and 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.

(Fatty acid ester)
Fatty acid esters are polycondensates of fatty acids and alcohols. As the fatty acid, a higher fatty acid having 12 or more carbon atoms is preferable because the dispersibility of the zinc oxide ultrafine particles in the coating liquid (a) is more excellent. Moreover, since the dispersibility of the zinc oxide ultrafine particles in the coating liquid (a) is more excellent, the alcohol is preferably a polyhydric alcohol, more preferably a polyalcohol. Examples of fatty acid esters include esters of polyglycerin and fatty acids.
The number average molecular weight of the fatty acid ester is preferably 300,000 or less, and 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.

<Zinc oxide ultrafine particles>
In the present invention, “ultrafine particle” means a particle having an average primary particle diameter of 1 nm to 1000 nm measured by a laser diffraction scattering method.
The average primary particle diameter 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 diameter of the zinc oxide ultrafine particles is preferably 5 nm or more. If the average primary particle diameter 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. Moreover, the transparency of the layer obtained by applying the coating liquid (a) to a substrate such as a film and drying it is excellent.
Therefore, the average primary particle diameter 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 FINEX 50 (manufactured by Sakai Chemical Industry Co., Ltd., average primary particle diameter 20 nm), ZINCOX SUPER F-2 (manufactured by Hakusui Tech Co., Ltd., average primary particle diameter 65 nm), and the like.

<Polyester resin>
The polyester resin is a polycondensate of a polyvalent carboxylic acid and a polyhydric alcohol. However, in this embodiment, the polyester acid resin is excluded.
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.

<Organic solvent>
An organic solvent is a liquid medium of an organic compound. Examples of the organic solvent include aliphatic hydrocarbons, alcohols, esters, ketones, glycol ethers, and aromatic hydrocarbons that are liquid at room temperature. Normal temperature means 1-30 degreeC.
Examples of the organic solvent include monovalent alcohols having 1 to 5 carbon atoms such as ethyl alcohol and isopropyl alcohol, ketones having 3 to 5 carbon atoms such as methyl ethyl ketone, esters having 4 to 7 carbon atoms such as ethyl acetate, and ethylene glycol. Examples thereof include glycol ethers having 4 to 7 carbon atoms such as monobutyl ether, and aromatic hydrocarbons having 7 to 9 carbon atoms such as toluene.
As the organic solvent, ethyl alcohol, methyl ethyl ketone and ethyl acetate which are easy to handle and excellent in volatility are preferable, and ethyl acetate is particularly preferable.
These organic solvents may be used individually by 1 type, and may use 2 or more types together.

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

<Content of each component in coating liquid (a)>
The solid content concentration of the coating liquid (a) is preferably 3 to 30% by mass, and more preferably 5 to 20% by mass. If solid content concentration is in the said range, coating property and liquid stability will be favorable.
The solid content concentration of the coating liquid (a) is a 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 all solid contents in the coating liquid (a). That is, the total mass of the dispersant in the coating liquid (a), the zinc oxide ultrafine particles, the polyester-based resin, and the other components that are solid (not including the other components that are solid) Including cases.)

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

  2-80 mass% is preferable with respect to the said solid content (100 mass%), and, as for content of the polyester-type resin in a coating liquid (a), 5-50 mass% is more preferable. When the content of the polyester resin is within the above range, the stretchability of the thermoforming gas barrier laminate having a layer formed from the coating liquid (a) is more excellent.

  Content of the dispersing agent in a coating liquid (a) is 1-40 mass parts with respect to 100 mass parts of zinc oxide ultrafine particles, and 2-30 mass parts is preferable. When the content of the dispersant 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. Moreover, the gas barrier property laminated body for thermoforming which has the layer formed from the coating liquid (a), and the gas barrier property of the molded product, and hot water resistance are excellent.

  The content of the dispersant in the coating liquid (a) is preferably 0.6 to 24% by mass and more preferably 1.2 to 18% by mass with respect to the solid content (100% by mass). When the content of the dispersant 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. Moreover, the gas barrier property laminated body for thermoforming which has the layer formed from the coating liquid (a), and the gas barrier property of the molded product, and hot water resistance are excellent.

  In the coating liquid (a), the content of a component that is a solid among the other components is preferably less than 10% by mass and more preferably less than 8% by mass with respect to the solid content (100% by mass). That is, the total amount of the dispersant, the zinc oxide ultrafine particles, and the polyester resin in the coating liquid (a) is preferably 90% by mass or more, more preferably 92% by mass or more with respect to the solid content (100% by mass). 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 a dispersant, zinc oxide ultrafine particles, a polyester resin, an organic solvent, and other components as necessary. 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 component described above can be mixed uniformly.

As an example of the preparation method of the coating liquid (a), zinc oxide ultrafine particles and a dispersing agent are added to an organic solvent, and agglomeration of primary particles of zinc oxide ultrafine particles is crushed and dispersed. A method of obtaining a coating liquid (a) by obtaining a dispersion, adding a polyester resin to the dispersion of ultrafine zinc oxide particles, and stirring the mixture is exemplified.
A bead mill, a high-speed stirrer, or the like can be used for crushing the aggregates when obtaining the zinc oxide ultrafine particle dispersion. In particular, use of a bead mill is preferred because the haze of the resulting thermoforming gas barrier laminate tends to be reduced.

<Effect>
The coating liquid (a) of the present invention contains a dispersant, zinc oxide ultrafine particles, a polyester resin, and an organic solvent, and the content of zinc oxide ultrafine particles is 20 to 90 with respect to the solid content. Since the content of the mass% and the dispersant 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.
The layer formed from the coating liquid (a) constitutes a gas barrier layer in combination with a layer containing a polycarboxylic acid polymer. The gas barrier laminate for thermoforming having such a gas barrier layer has high thermoformability, and is subjected to thermoforming with stretching such as making into a container shape, and then heat sterilization treatment such as retort treatment and boil treatment. After performing the above, excellent gas barrier properties are exhibited.
The reason for the above effect is that one or more selected from amine salts of polyester acid resins, polyether phosphate resins (excluding amine salts), and fatty acid esters are used as dispersants for ultrafine zinc oxide particles. As a result, the dispersion state of the zinc oxide ultrafine particles in the coating liquid (a) can be stably maintained as smaller particles, and thereby the zinc oxide ultrafine particles are small in the layer formed from the coating liquid. It is mentioned that the particles are uniformly distributed and the state is sufficiently maintained even after thermoforming.
Because zinc oxide ultrafine particles are uniformly distributed as small particles, the reaction between zinc oxide and polycarboxylic acid-based polymer (polycarboxylic acid-based polymer) uniformly over the entire in-plane direction of the gas barrier layer during heat sterilization treatment It is considered that ion crosslinking by the zinc ion of the polymer occurs and the reaction is more likely to proceed.
If one or more selected from amine salts of polyester acid resins, polyether phosphate resins (excluding amine salts), and fatty acid esters are not used as the dispersant, the dispersibility of the zinc oxide ultrafine particles deteriorates. It is conceivable that the zinc oxide ultrafine particles are aggregated during the preparation of the coating liquid and the particle diameter of the zinc oxide ultrafine particles is increased, so that the liquid stability of the coating liquid is deteriorated and the liquid preparation becomes difficult.

[Gas barrier laminate for thermoforming]
Embodiments 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 thermoforming gas barrier laminate 10 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 base material 1, the layer (B) 3, and the layer (A) 4 are laminated in this order.

<Base material>
The substrate 1 is capable of thermoforming and serves as a support for laminating the layer (A) 4, the layer (B) 3, and the like.
Although it does not specifically limit as a material which comprises the base material 1, From the point of the suitability as a packaging material, when using the gas-barrier laminated body 10 for thermoforming as a packaging material, a polyester-type polymer, a polyamide-type polymer, Polyolefin polymers are preferred.
Examples of the polyester polymer include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyε-caprolactone, polyhydroxybutyrate, polyhydroxyvalylate, and copolymers thereof. Examples of polyamide polymers include nylon 6, nylon 66, nylon 12, nylon 6,66 copolymer, nylon 6,12 copolymer, metaxylene adipamide / nylon 6 copolymer, and copolymers thereof. Is mentioned. Examples of the polyolefin polymer include low density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, poly-4-methylpentene, cyclic polyolefin, copolymers thereof, and acid-modified products thereof.

Although it does not specifically limit as a form of the base material 1, It can use with forms, such as an unstretched sheet and an unstretched film.
The base material 1 may be comprised from the single layer, and may be comprised from the several layer.
The surface of the substrate 1 may be subjected to a surface activation treatment such as a corona treatment, a flame treatment, or a plasma treatment.
Although the thickness of the base material 1 is not specifically limited, It is preferable to exist in the range of 5-500 micrometers, and it is more preferable to exist in the range of 10-300 micrometers. If the thickness of the substrate 1 is less than the lower limit of the range, there is a tendency for coating properties such as the substrate 1 to be easily cut. On the other hand, if the thickness exceeds the upper limit of the range, the rigidity of the substrate 1 is increased. Since it is too high, it tends to cause a problem in handling in secondary processing and filling of contents.

<Layer (A)>
The layer (A) 4 includes a dispersant, ultrafine zinc oxide particles, and a polyester resin. The layer (A) 4 may further contain other components other than the dispersant and the zinc oxide ultrafine particles, the polyester-based resin, and the organic solvent, if necessary.
The dispersant, zinc oxide ultrafine particles, polyester resin, and 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, and preferably 30 to 80% by mass with respect to 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.

  2-80 mass% is preferable with respect to the total mass (100 mass%) of layer (A) 4, and, as for content of the polyester-type resin in layer (A) 4, 5-50 mass% is more preferable. 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 dispersant in the layer (A) 4 is 1 to 40 parts by mass, and preferably 2 to 30 parts by mass with respect to 100 parts by mass of the zinc oxide ultrafine particles. If the content of the dispersant is within the above range, the zinc oxide ultrafine particles are uniformly distributed as small particles in the layer (A) 4, and the gas barrier properties and heat resistance of the thermoforming gas barrier laminate 10 and its molded product are distributed. Excellent aqueous properties.

  The content of the dispersant in the layer (A) 4 is preferably 0.6 to 24% by mass and more preferably 1.2 to 18% by mass with respect to the total mass (100% by mass) of the layer (A) 4. . If the content of the dispersant is within the above range, the zinc oxide ultrafine particles are uniformly distributed as small particles in the layer (A) 4, and the gas barrier properties and heat resistance of the thermoforming gas barrier laminate 10 and its molded product are distributed. Excellent aqueous properties.

  In the layer (A) 4, the content of the component that is solid among the other components is preferably less than 10% by mass and more preferably less than 8% by mass with respect to the total mass (100% by mass) of the layer (A) 4. preferable. That is, the total amount of the dispersant, the zinc oxide ultrafine particles, and the polyester resin in the layer (A) 4 is preferably 90% by mass or more with respect to the total mass (100% by mass) of the layer (A) 4. The mass% or more is more preferable.

The layer (A) 4 is typically a layer formed from the coating liquid (a).
A 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 relative 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 ultrafine zinc oxide particles. The same applies to the contents of the dispersant, the polyester resin, and the other components.

  The thickness of the layer (A) 4 (the thickness of the thermoforming gas barrier laminate 10 before thermoforming) is preferably in the range of 0.05 to 50 μm, and preferably in the range of 0.1 to 10 μm. More preferably, it is particularly preferably in the range of 0.2 to 5 μm. When the thickness of the layer (A) 4 is less than the lower limit of the above range, the gas barrier properties of the thermoforming gas-barrier laminate 10 and the molded product tend to be insufficient, while when exceeding the upper limit of the above range, Formability tends to be poor.

<Layer (B)>
Layer (B) 3 contains a polycarboxylic acid polymer.
The 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 viewpoints of gas barrier properties and hot water resistance. It is preferable.
The layer (B) 3 preferably contains a plasticizer (ii) from the viewpoint of stretchability.
The layer (B) 3 may further contain other components other than the polycarboxylic acid polymer, the silicon-containing compound (i), and the plasticizer (ii) as necessary.

(Polycarboxylic acid polymer)
The polycarboxylic acid polymer refers to a polymer having two or more carboxyl groups in one molecule and having no ester bond in the main chain.
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, Examples include acidic polysaccharides having a carboxyl group in the molecule such as pectin.

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. C3-C5 (C3-C5) ethylenically unsaturated carboxylic acids such as acrylic acid and methacrylic acid are preferred.
Examples of other ethylenically unsaturated monomers copolymerizable with the ethylenically unsaturated carboxylic acid include acrylamide, methacrylamide, acrylonitrile, methyl acrylate, ethyl acrylate, methyl methacrylate, hydroxyethyl acrylate, and hydroxyethyl methacrylate. C3 to C5 ethylenically unsaturated carboxylic acid amides, nitriles or esters, or vinyl acetate, 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, ethylene, propylene, styrene, α-methylstyrene, Examples thereof include nuclear methyl-substituted styrene.

As the polycarboxylic acid polymer, poly (meth) acrylic acid is preferable.
Poly (meth) acrylic acid here is a polymer having two or more (meth) acrylic acid units. The (meth) acrylic acid unit represents one or both of an acrylic acid unit and a methacrylic acid unit.
Examples of poly (meth) acrylic acid include the following.
Acrylic acid or methacrylic acid homopolymer (polyacrylic acid, polymethacrylic acid),
A copolymer of acrylic acid and methacrylic acid,
(Meth) 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 the ethylenically unsaturated carboxylic acid,
Copolymers of (meth) acrylic acid, ethylenically unsaturated carboxylic acids other than (meth) acrylic acid, and other ethylenically unsaturated monomers copolymerizable with ethylenically unsaturated carboxylic acid.

When poly (meth) acrylic acid has an ethylenically unsaturated carboxylic acid unit other than (meth) acrylic acid, the ratio of the ethylenically unsaturated carboxylic acid unit in poly (meth) acrylic acid is not particularly limited, Any ratio may be used.
If the poly (meth) acrylic acid has other ethylenically unsaturated monomer units copolymerizable with the ethylenically unsaturated carboxylic acid, that is, units having no carboxyl group, the poly (meth) acrylic acid The ratio of the other ethylenically unsaturated monomer units is set within a range not inhibiting the water solubility of poly (meth) acrylic acid, and preferably 20% by mass with respect to the total mass (100% by mass) of all units. It is as follows.

  Poly (meth) acrylic acid is a method of polymerizing (meth) acrylic acid and, if necessary, ethylenically unsaturated carboxylic acid other than (meth) acrylic acid, other ethylenically unsaturated monomers, poly (meta) ) It can be produced by a method of saponifying an acrylic ester. The polymerization method is not particularly limited, and a known polymerization method such as bulk polymerization, aqueous solution polymerization, polymerization in an organic solvent, or irradiation polymerization can be used. What was manufactured by any method is applicable to this invention. When the layer (B) is formed using the coating liquid (b), since the polycarboxylic acid polymer is usually used as an aqueous solution, aqueous solution polymerization is industrially advantageous.

The polycarboxylic acid 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, and zinc. Examples of such metal compounds include sodium hydroxide, calcium hydroxide, calcium oxide, and zinc oxide.
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 polymer is preferably in the range of 10,000 to 10,000,000, and in the range of 50,000 to 1,000,000 from the viewpoint of the formability of the organic thin film. More preferably, it is within. If it is less than the lower limit of the range, the thermoforming gas barrier laminate obtained tends to have poor thermoformability, and if it exceeds the upper limit of the range, the formability of the thin film tends to be impaired.

(Silicon-containing compound (i))
The silicon-containing compound (i) is composed of 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 is further improved. Moreover, since hot water resistance can be imparted without impairing moldability, the occurrence frequency 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, γ-isocyanatopropyltrisilane. Examples include methoxysilane and γ-isocyanatopropyltriethoxysilane. 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 subjecting a silane coupling agent to hydrolysis and condensation using, for example, 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 substituted with a hydroxyl group to become a hydrolyzate. Further, the hydrolyzate condenses to form a compound in which silicon atoms (Si) are bonded through oxygen. By repeating this condensation, a hydrolysis condensate is obtained.

In general, a silane coupling agent is easily hydrolyzed and a condensation reaction easily occurs in the presence of an acid or an alkali. Therefore, only a silane coupling agent, only a hydrolyzate thereof, or a condensate thereof. It is rare to exist alone. 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 hydrolysis condensate.

When the silicon-containing compound (i) is contained in the layer (B), the content of the silicon-containing compound (i) is the mass of the polycarboxylic acid polymer from the viewpoint of gas barrier properties of the thermoforming gas barrier laminate 10. And the ratio of the mass of the silicon-containing compound (i) (polycarboxylic acid 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 a 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 the same as that of the silane coupling agent. The converted value, that is, the amount of the silane coupling agent charged.

(Plasticizer (ii))
The plasticizer (ii) can be appropriately selected from known materials and used.
Specific examples of the plasticizer (ii) include, for example, ethylene glycol, trimethylene glycol, propylene glycol, tetramethylene glycol, 1,3-butanediol, 2,3-butanediol, pentamethylene glycol, hexamethylene glycol, 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, phthalic acid ester and the like. Among these, glycerin, polyglycerin, ethylene glycol, polyethylene glycol, and the like are preferable from the viewpoint of thermoformability of the thermoforming gas barrier laminate 10 and gas barrier properties of the molded body. These materials may be used alone or in combination of two or more.

  When the layer (B) contains the plasticizer (ii), the content of the plasticizer (ii) is the ratio of the mass of the polycarboxylic acid polymer to the mass of the plasticizer (ii) (polycarboxylic acid-based weight). The amount of the combined / silicon-containing compound (i)) is preferably 95/5 to 80/20, and more preferably 95/5 to 85/15. When the ratio is in the above range, both the thermoformability of the thermoforming gas barrier laminate 10 and the gas barrier properties of the molded body can be achieved. That is, when the polycarboxylic acid polymer is sufficiently present in the layer (B) 3, it is derived from the polycarboxylic acid polymer in the layer (B) 3 and the zinc oxide ultrafine particles in the layer (A). A stable gas barrier property can be expressed by forming an ionic bond with the zinc ion. 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 improved.

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

  The thickness of the layer (B) 3 (thickness before thermoforming of the thermoforming gas barrier laminate 10) is preferably in the range of 0.01 to 20 μm, and in the range of 0.05 to 10 μm. More preferably, it is particularly preferably in the range of 0.1 to 5 μm. When the thickness of the layer (B) 3 is less than the lower limit of the range, film formation tends to be difficult. On the other hand, when the thickness exceeds the upper limit of the range, the ion-bonding reaction with zinc ions is uniform in the thickness direction. Since it becomes difficult to advance, the gas barrier property of the obtained molded product tends to be insufficient.

<Coating liquid (b)>
The coating liquid (b) contains a polycarboxylic acid 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 viewpoints of gas barrier properties and hot water resistance. It is preferable.
The coating liquid (b) preferably contains a plasticizer (ii) from the viewpoint of stretchability.
The coating liquid (b) may further contain other components other than the polycarboxylic acid polymer, the silicon-containing compound (i), the plasticizer (ii), and the liquid medium as necessary.

  The polycarboxylic acid polymer, the silicon-containing compound (i), the plasticizer (ii), and other components are the same as those described 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 performing the hydrolysis reaction is usually required when it contains a silane coupling agent. 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 the solubility and cost of the polycarboxylic acid polymer, and in terms of improving the solubility of the silane coupling agent and the coating property of the coating liquid (b), alcohol or the like. Organic solvents are preferred. Therefore, a mixed solvent of water and an organic solvent is particularly preferable.

As the water, purified water is preferable. 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 a 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 is present in an amount of 20 to 95% by mass, and the organic solvent is present in an amount of 80 to 5% by mass (provided that the total of water and the organic solvent is 100% by mass). preferable.

When the silicon-containing compound (i) is contained in the coating liquid (b), the ratio of the mass of the polycarboxylic acid polymer to the mass of the silicon-containing compound (i) (polycarboxylic acid polymer / silicon-containing compound (i )) Is preferably 99.5 / 0.5 to 80.0 / 20.0 from the viewpoint of gas barrier properties of the thermoforming gas barrier laminate 10.
However, the mass of the silicon-containing compound (i) other than the silane coupling agent is a 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 the same as that of the silane coupling agent. The converted value, that is, the amount of the silane coupling agent charged.

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

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 viewpoints of gas barrier properties and coating properties. Particularly preferred.
The solid content concentration of the coating liquid (b) is a 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 all solid contents in the coating liquid (b). That is, the total mass of the polycarboxylic acid polymer in the coating liquid (b) and the additives (silicon-containing compound (i), plasticizer (ii), and other components) included as necessary.

  When the layer (B) 3 is a layer formed from the coating liquid (b), the content of the polycarboxylic acid polymer relative 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 polymer relative to the solid content. The same applies to the contents of the silicon-containing compound (i), the plasticizer (ii), and other components.

<Application>
The gas barrier laminate 10 for thermoforming is used for thermoforming. In the present specification and claims, “thermoforming” means molding accompanied by stretching of a gas barrier laminate for thermoforming under heating.
The thermoforming gas barrier laminate 10 is formed into a molded product by thermoforming. For example, the gas barrier laminate 10 for thermoforming is heated, and in this state, the gas barrier laminate 10 for thermoforming is stretched and formed into an arbitrary shape to obtain a molded product. Such a molded article includes a thermoforming gas barrier laminate 10 at least partially stretched. Examples of molded products include molded containers and bags.

<The manufacturing method of the gas-barrier laminated body for thermoforming of 1st 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 substrate 1.
(Α2): A step of forming the layer (A) 4 on the surface of the substrate 1 on which the layer (B) 3 is formed.

(Process (α1))
Although there is no limitation in particular as a formation method of a layer (B), For example, the method of apply | coating a coating liquid (b) on the base material 1, and drying is mentioned.

  The coating method for the coating liquid (b) is not particularly limited. For example, the casting method, dipping method, roll coating method, gravure coating method, screen printing method, reverse coating method, spray coating method, kit coating method, die coating method. , Metal ring 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 layer (B) 3 is formed on the base material 1 by removing the liquid medium of the coating liquid (b) by drying.
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. Although there is no limitation in particular as drying temperature, Usually, 50-160 degreeC is preferable when a liquid medium is the mixed solvent of water mentioned above or water and an organic solvent. The drying is usually preferably performed under normal pressure or reduced pressure, and is preferably performed at normal pressure from the viewpoint of facility simplicity.

In the case where the silicon-containing compound (i) is contained in the coating liquid (b), 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 (or The heat treatment may be performed at the time of almost complete).
The heat treatment is usually performed at a temperature of 120 to 240 ° C., preferably 150 to 230 ° C., and usually 10 seconds to 30 minutes, preferably 20 seconds to 20 minutes.
The drying and heat treatment have portions where conditions such as temperature overlap, but these do not need to be clearly distinguished and may be performed continuously.

(Process (α2))
Although there is no limitation in particular as a formation method of layer (A) 4, For example, the method of apply | coating a coating liquid (a) on a base material and drying is mentioned.

  The coating method of the coating liquid (a) is not particularly limited. 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. , Metal ring bar coating method, chamber doctor combined coating method, curtain coating method and the like.

After coating the coating liquid (a) on the layer (B) 3, the liquid medium of the coating liquid (a) is removed by drying, whereby the layer (A) 4 is formed on the layer (B) 3. . Thereby, 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. Although there is no limitation in particular as drying temperature, Usually, 50-160 degreeC is preferable when a liquid medium is an organic solvent. 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. The drying is usually preferably performed under normal pressure or reduced pressure, and is preferably performed at normal pressure from the viewpoint of facility simplicity.

<Effect>
In the thermoforming gas barrier laminate 10, the gas barrier layer 2 on the substrate 1 includes a dispersant, zinc oxide ultrafine particles, and a polyester resin, and the content of zinc oxide ultrafine particles is a solid content. 20 to 90% by mass with respect to 100% by mass of the zinc oxide ultrafine particles, and the dispersant (A) 4 and the polycarboxylic acid polymer are included. Since it has layer (B) 3, it is excellent in thermoformability. For this reason, a molded body obtained by thermoforming the gas barrier laminate 10 for thermoforming into a container shape or the like has an excellent gas barrier property because a decrease in gas barrier properties due to thermoforming is suppressed.
The reason for the above effect is that the coating liquid for forming the layer (B) is an amine salt of a polyester acid resin, a polyether phosphate resin (excluding amine salts), a fatty acid as a dispersant for ultrafine zinc oxide particles. Since it contains one or more selected from esters, the dispersibility is good, and as described above, it is considered that the zinc oxide ultrafine particles in the layer (B) are uniformly distributed as small particles. .

<< Second Embodiment >>
FIG. 2 is a cross-sectional view schematically showing the gas barrier laminate 20 for thermoforming according to the first embodiment of the present invention. In the following embodiment, the same reference numerals are given to the components already described, and the detailed description thereof is 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 substrate 1 and the gas barrier layer 2. is there.

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

The anchor coat layer 5 preferably includes a polyurethane resin among the resins.
As the polyol constituting the polyurethane resin, a polyester-based polyol is preferable. That is, among polyurethane resins, polyester polyurethane resins are preferable. Examples of the polyester-based polyol include a reaction product of a polyvalent carboxylic acid or the like and a glycol.
Examples of the polyisocyanate constituting the polyurethane resin include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene. Examples include range isocyanate and isophorone diisocyanate.
The anchor coat layer 5 may contain a carbodiimide group-containing resin from the viewpoint of adhesion with 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 as necessary. Examples of the silane coupling agent are the same as those described for the silicon-containing compound (i) described later.

  The thickness of the anchor coat layer 5 (thickness before thermoforming of the thermoforming gas barrier laminate 20) is not particularly limited, but is preferably in the range of 0.01 to 5 μm, preferably 0.03 to 3 μm. Is more 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. On the other hand, if the thickness exceeds the upper limit of the above range, the desired gas barrier property tends not to be developed.

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

<The manufacturing method of the gas-barrier laminated body for thermoforming of 2nd embodiment>
Examples of a 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 substrate 1.
(Β2): A step of forming the layer (B) 3 on the surface of the base material 1 on which the anchor coat layer 5 is formed.
(Β3): A step of forming the layer (A) 4 on the surface of the substrate 1 on which the anchor coat layer 5 and the layer (B) 3 are formed.

(Process (β1))
The formation method of the anchor coat layer 5 is not particularly limited, and a known method can be appropriately selected. For example, the anchor coat layer can be formed by applying an anchor coat agent and drying.
Examples of the anchor coat agent used for forming the anchor coat layer include those containing the aforementioned resin or a precursor thereof, a solvent, and, if necessary, an additive. The resin or its precursor is preferably a polyurethane-based, polyester-based or acrylic-based polymer material. Among them, a two-component solution comprising a main component containing a polyester-based polyol, which is a polyurethane-based polymer material, and a curing agent containing an isocyanate. A type anchor coating agent is preferred.
The application and drying of the anchor coating agent can be performed in the same manner as the application and drying of the coating liquid (a) in the aforementioned step (α2).

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

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

<Effect>
In the thermoforming gas barrier laminate 20, since the gas barrier layer 2 on the substrate 1 has the layer (A) 4 and the layer (B) 3 in the same manner as the thermoforming gas barrier laminate 10, Excellent thermoformability. Moreover, since the interlayer adhesive strength between the base material 1 and the gas barrier layer 2 can be increased by having the anchor coat layer 5, the thermoformability is further improved.

≪Third embodiment≫
FIG. 3 is a sectional view schematically showing a thermoforming gas barrier laminate 30 according to the third embodiment of the present invention.
The gas barrier laminate 30 for thermoforming 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. 6 and 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 thermoforming gas barrier laminate 30 further includes an adhesive layer 6 and a sealant layer 7.
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 in accordance with purposes such as imparting abrasion resistance, glossiness, imparting heat sealability, imparting strength, and moisture resistance to the gas barrier laminate 30 for thermoforming. Layer.

The sealant layer 7 includes a thermoplastic resin.
The thermoplastic resin in the sealant layer 7 can be appropriately determined in consideration of heat sealing properties and stretch moldability, and examples thereof include polyester polymers, polyamide polymers, polyolefin polymers, and the like. Specific examples of these polymers are the same as those mentioned for the substrate 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 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 (the thickness of the thermoforming gas barrier laminate 30 before thermoforming) is appropriately determined according to the thickness of the molded product, etc., but is preferably 1 to 2000 μm, More preferably, it is 1500 μm. If the thickness of the sealant layer 7 is not more than the upper limit of the above range, the gas barrier properties are good. If the thickness of the sealant layer 7 is equal to or greater than the lower limit of the above range, molding defects such as pinholes hardly occur during thermoforming, and thermoformability is good.

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

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

<The manufacturing method of the gas-barrier laminated body for thermoforming of 3rd embodiment>
Examples of a 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 substrate 1.
(Γ2): A step of forming the layer (B) 3 on the surface of the base material 1 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 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 (laminate surface) of the base material 1 on which the anchor coat layer 5, the layer (B) 3 and the layer (A) 4 are formed. Process.

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

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

(Process (γ2))
The step (γ2) can be performed in the same manner as the above-described step (β2).
When the silicon-containing compound (i) is contained in the coating liquid (b) used in the step (γ2), 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. In the case of performing the heat treatment, the heat treatment may be performed at the time when the drying is completed (or almost completed) as described above, or may be performed at the time when the aging treatment described later is completed.

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

(Process (γ4))
The method for laminating the thermoplastic resin film is not particularly limited, and a known method can be used as appropriate. 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 as necessary. For example, a thermoplastic resin film can be adhered to the surface of the layer (A) 4 by a dry lamination method using an adhesive. When the adhesive is used, the adhesive layer 6 is formed between the layer (A) 4 and the thermoplastic resin film (sealant layer 7). As the adhesive, known adhesives as described above can be used.

  An aging treatment may be performed after laminating the thermoplastic resin film in the step (γ4). Examples of the aging treatment include a treatment of holding at a temperature of 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, since the gas barrier layer 2 on the substrate 1 has the layer (A) 4 and the layer (B) 3 in the same manner as the thermoforming gas barrier laminate 20, Excellent thermoformability. Moreover, since the interlayer adhesive strength between the base material 1 and the gas barrier layer 2 can be increased by having the anchor coat layer 5, the thermoformability is further improved.
Furthermore, in the gas barrier laminate 30 for thermoforming, the sealant layer 7 can provide wear resistance, gloss, heat sealability, strength, moisture resistance, and the like. For example, when the molded container is thermoformed so that the surface on the sealant layer 7 side of the gas barrier laminate 30 for thermoforming becomes the sealing surface of the molded container, the contents are stored in the molded container, and then the lid material, etc. Can be used as a packaging material.

As mentioned above, although embodiment was shown and the gas-barrier laminated body for thermoforming of this invention was demonstrated, this invention is not limited to the said embodiment. Each configuration in the above embodiment, a combination thereof, and the like are examples, and the addition, omission, replacement, and other modifications of the configuration can be made without departing from the spirit of the present invention.
For example, the layer configuration of the gas barrier layer in the gas barrier laminate for thermoforming of the present invention is the layer (B) and the layer in order from the substrate 1 side as in the gas barrier layer 2 shown in the first to third embodiments. It is not limited to what (A) laminated | stacked (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) may not be adjacent to each other. The layer (A) and the layer (the layer (A) and the layer ( It is preferable that at least one layer constituting unit adjacent to B) is included. A layer structure including at least one layer structural unit in which layer (A), layer (B), and layer (A) are adjacent or layer (B), layer (A), and layer (B) are adjacent to each other preferable.

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

[Molded body]
Embodiments of the molded product of the present invention will be described.

≪Fourth embodiment≫
FIG. 4 is a top view showing a molded container 11 (molded product) according to the 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 includes a container body 12 that is round when viewed from above.

  The container main body 12 has a circular bottom 12a, a peripheral wall 12b that rises from the periphery of the bottom 12a, and a flange 12c that extends substantially horizontally from the outer peripheral surface of the upper edge of the peripheral wall 12b. The peripheral wall 12b is formed in an inverted truncated cone shape whose outer diameter gradually increases toward the upper edge.

In the container main body 12, an opening is formed by the upper edge of the peripheral wall portion 12b, and a region surrounded by the bottom portion 12a and the peripheral wall portion 12b is an accommodating portion for accommodating contents.
Although the diameter W of the opening part of the container main body 12 is not specifically limited, For example, it can be set as 20-300 mm.
Although the depth D of the accommodating part of the container main body 12 is not specifically limited, For example, it can be 20-100 mm.

The container body 12 uses the thermoforming gas barrier laminate 30. That is, it is composed of a thermoformed gas barrier laminate 30 that is thermoformed.
In the container main body 12, the thermoforming gas barrier laminate 30 is arranged with the substrate 1 side facing the outside of the container main body 12 and the sealant layer 7 side facing the inside of the container main body 12. Therefore, the upper surface of the flange portion 12 c is composed of the sealant layer 7. Thus, after the contents are accommodated in the accommodating portion, the opening portion is covered with a lid member or the like, and the opening portion can be sealed by heat sealing.

<Method for Manufacturing Molded Container of Fourth Embodiment>
The molded container 11 (container main body 12) can be manufactured by thermoforming the gas barrier laminate 30 for thermoforming.
As a manufacturing method of the molded container 11, a manufacturing method including a step of heating the thermoforming gas barrier laminate 30 and drawing it into a container shape to obtain the 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 in which the thermoforming gas barrier laminate 30 is heat-softened using a vacuum forming machine and vacuum-formed. Specifically, the gas barrier laminate 30 for thermoforming is heated and softened for about 5 to 30 seconds in a heating furnace set to 400 to 500 ° C. The temperature of the gas barrier laminate 30 for thermoforming can be adjusted by the heating temperature and heating time at this time. Immediately after heating, the thermoforming gas barrier laminate 30 is placed on a mold (resin mold or metal mold) having an arbitrary shape, and the air between the thermoforming gas barrier laminate 30 and the mold is sucked. The gas barrier laminate 30 for thermoforming is brought into close contact with a mold, cooled and molded into a mold shape.
However, the stretch molding method is not limited to this. The molding machine is not limited to a vacuum molding machine, and a pressure forming machine, a melt molding machine, or the like may be used. Further, if necessary, a known molding method such as a method of molding into a mold shape that further uses a plug (straight method, drape method, air slip method, snapback method, plug assist method) or the like can be used.

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

The heat sterilization treatment is a treatment that is exposed to a high-temperature and high-humidity atmosphere or 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 for the heat sterilization treatment is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, from the viewpoint of gas barrier properties.
Furthermore, when the heat sterilization treatment is a treatment in which the molded container is exposed to an atmosphere of high temperature and high humidity, the relative humidity of the atmosphere is preferably 90% or more.

The heat sterilization treatment may be performed before the contents are stored in the molded container 11, or may be performed after the contents are stored and the opening is sealed with a lid as necessary. When performing after accommodating the contents, the heat sterilization treatment can also serve as the heat sterilization treatment of the contents.
Specific examples of contents requiring heat sterilization include, for example, seasoned foods (curry, stew, etc.), cooked foods for microwave ovens (baby food, cooked rice, ladymeal, etc.), soups, desserts, pets Foods (especially wet type), processed agricultural and livestock products, and the like can be mentioned.
The molded container 11 can be suitably used as a food packaging container as mentioned in the above example.
The lid member preferably has a sealant layer on the surface (seal surface) that contacts the molded container 11, and the sealant layer contains the same kind of thermoplastic resin as the thermoplastic resin of the sealant layer 7 of the molded container 11. . For example, if the thermoplastic resin of the sealant layer 7 of the molded container 11 is a polypropylene polymer, the thermoplastic resin of the sealant layer of the lid is also preferably a polypropylene polymer. The shape of the lid member is not particularly limited, and may be a sheet shape or a three-dimensional shape.

As mentioned above, although the embodiment was shown and the compact of the present invention was explained, the present invention is not limited to the above-mentioned embodiment. Each configuration in the above embodiment, a combination thereof, and the like are examples, and the addition, omission, replacement, and other modifications of the configuration can be made without departing from the spirit of the present invention.
For example, the molded product of the present invention is not limited to the molded container shown in the fourth embodiment. For example, the shape of the molded container in a top view of the container body may be a shape other than the round shape as described above, for example, a polygonal shape such as a square shape. The cross-sectional shape may be a line-symmetric shape as described above or an asymmetric shape. Further, the molded container may be a form in which two or more containers are connected in addition to a single container (container body 12) such as the molded container 11. 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 the molded product other than the molded container 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.

<Materials used>
Zinc oxide ultrafine particles: FINEX50 manufactured by Sakai Chemical Industry Co., Ltd., average primary particle size 20 nm.
Amine salt of polyester acid resin (1): DA-7301 manufactured by Enomoto Kasei Co., Ltd., solid content concentration 75% by mass (diluting solvent: alkylcyclohexane, methyl ether of propylene glycol).
Polyether phosphate ester-based resin (excluding amine salts) (2): DA-375 manufactured by Enomoto Kasei Co., solid content concentration: 100% by mass.
Fatty acid ester (3): PA-111 manufactured by Ajinomoto Fine Techno Co., solid content concentration: 100% by mass.
Amine salt of polyether phosphate ester resin (4): DA-325 manufactured by Enomoto Kasei Co., Ltd., solid content concentration: 100% by mass.
Sodium polycarboxylate (5): Poise 521 manufactured by Kao Corporation, solid concentration 40% by mass, average molecular weight 20,000 (diluting solvent: water).
Polyester resin (6): Elitel UE-3220 manufactured by Unitika, solid content concentration 20% by mass (diluting solvent: ethyl acetate).
Polyester resin (7): Takelac A525 manufactured by Mitsui Chemicals, solid content concentration 50% by mass (diluting solvent: ethyl acetate).
Polyester resin (8): Elitel KT-8803 manufactured by Unitika 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 mg KOH / g).

<Preparation of coating solution>
(Preparation Example 1)
To 74.7 g of ethyl acetate, 20 g of ultrafine zinc oxide particles and 5.3 g of the polyester acid resin amine salt (1) as a dispersant were added and stirred thoroughly with a stirrer. After sufficiently dispersing with 0.3 mm diameter zirconia beads (Fritsch P-7), the zirconia beads were separated with 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 (6) are added and stirred to obtain a coating liquid (a-1) (solid content concentration of 15% by mass). It was.

(Preparation Example 2)
To 74.7 g of ethyl acetate, 20 g of ultrafine zinc oxide particles and 5.3 g of the polyester acid resin amine salt (1) as a dispersant were added and stirred thoroughly with a stirrer. After sufficiently dispersing with 0.3 mm diameter zirconia beads (Fritsch P-7), the zirconia beads were separated with a sieve to obtain a zinc oxide ultrafine particle dispersion. To 9.0 g of this zinc oxide ultrafine particle dispersion, 6.8 g of ethyl acetate and 4.2 g of polyester resin (6) are added and stirred to obtain a coating liquid (a-2) (solid content concentration of 15% by mass). It was.

(Preparation Example 3)
To 77.9 g of ethyl acetate, 20 g of zinc oxide ultrafine particles and 2.1 g of a polyester acid resin amine salt (1) as a dispersant were added and stirred thoroughly with a stirrer. After sufficiently dispersing with 0.3 mm diameter zirconia beads (Fritsch P-7), the zirconia beads were separated with a sieve to obtain a zinc oxide ultrafine particle dispersion. To 13.5 g of this zinc oxide ultrafine particle dispersion, 6.1 g of ethyl acetate and 0.42 g of polyester resin (6) are added and stirred to obtain a coating liquid (a-3) (solid content concentration 15% by mass). It was.

(Preparation Example 4)
To 79.7 g of ethyl acetate, 20 g of zinc oxide ultrafine particles and 0.27 g of amine salt (1) of polyester acid resin as a dispersing agent were added and stirred thoroughly with a stirrer. After sufficiently dispersing with 0.3 mm diameter zirconia beads (Fritsch P-7), the zirconia beads were separated with a sieve to obtain a zinc oxide ultrafine particle dispersion. To 9.0 g of this zinc oxide ultrafine particle dispersion, 5.1 g of ethyl acetate and 5.9 g of polyester resin (6) are added and stirred to obtain a coating liquid (a-4) (solid content concentration 15% by mass). It was.

(Preparation Example 5)
To 70.7 g of ethyl acetate, 20 g of ultrafine particles of zinc oxide and 9.3 g of amine salt (1) of polyester acid resin as a dispersant were added and stirred well with a stirrer. After sufficiently dispersing with 0.3 mm diameter zirconia beads (Fritsch P-7), the zirconia beads were separated with a sieve to obtain a zinc oxide ultrafine particle dispersion. To 9.0 g of this zinc oxide ultrafine particle dispersion, 8.15 g of ethyl acetate and 2.85 g of polyester resin (6) are added and stirred to obtain a coating liquid (a-5) (solid content concentration of 15% by mass). It was.

(Preparation Example 6)
To 74.7 g of ethyl acetate, 20 g of ultrafine zinc oxide particles and 5.3 g of the polyester acid resin amine salt (1) as a dispersant were added and stirred thoroughly with a stirrer. After sufficiently dispersing with 0.3 mm diameter zirconia beads (Fritsch P-7), the zirconia beads were separated with a sieve to obtain a zinc oxide ultrafine particle dispersion. To 9.0 g of this zinc oxide ultrafine particle dispersion, 9.3 g of ethyl acetate and 1.7 g of polyester resin (7) are added and stirred to obtain a coating liquid (a-6) (solid content concentration 15% by mass). It was.

(Preparation Example 7)
To 76 g of ethyl acetate, 20 g of zinc oxide ultrafine particles and 4 g of polyether phosphate ester resin (excluding amine salt) (2) as a dispersant were added and sufficiently stirred with a stirrer. Was sufficiently dispersed using a zirconia bead having a diameter of 0.3 mm with a planetary ball mill (Fritsch P-7), and then 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, 6.8 g of ethyl acetate and 4.2 g of polyester resin (6) are added and stirred to obtain a coating liquid (a-7) (solid content concentration of 15% by mass). It was.

(Preparation Example 8)
After adding 20 g of zinc oxide ultrafine particles and 4 g of fatty acid ester (3) as a dispersing agent to 76 g of ethyl acetate and stirring well with a stirrer, 30.0 g of this was mixed with a planetary ball mill (Fritsch P-7). After sufficiently dispersing 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, 6.8 g of ethyl acetate and 4.2 g of polyester resin (6) are added and stirred to obtain a coating liquid (a-8) (solid content concentration 15% by mass). It was.

(Preparation Example 9)
To 74.7 g of ethyl acetate, 20 g of ultrafine zinc oxide particles and 5.3 g of the polyester acid resin amine salt (1) as a dispersant were added and stirred thoroughly with a stirrer. After sufficiently dispersing with 0.3 mm diameter zirconia beads (Fritsch P-7), the zirconia beads were separated with a sieve to obtain a zinc oxide ultrafine particle dispersion. To 0.75 g of this zinc oxide ultrafine particle dispersion, 5.2 g of ethyl acetate and 14.1 g of polyester resin (6) are added and stirred to obtain a coating liquid (a-9) (solid content concentration 15% by mass). It was.

(Preparation Example 10)
After adding 20 g of zinc oxide ultrafine particles and 0.8 g of polyester acid resin amine salt (1) as a dispersing agent to 79.2 g of ethyl acetate and stirring well with a stirrer, 30.0 g of this was planetary ball mill. After sufficiently dispersing with 0.3 mm diameter zirconia beads (Fritsch P-7), the zirconia beads were separated with a sieve to obtain a zinc oxide ultrafine particle dispersion. To 14.3 g of this zinc oxide ultrafine particle dispersion, 5.4 g of ethyl acetate and 0.32 g of polyester resin (6) are added and stirred to obtain a coating liquid (a-10) (solid content concentration of 15% by mass). It was.

(Preparation Example 11)
After adding 20 g of zinc oxide ultrafine particles to 80 g of ethyl acetate and sufficiently stirring with a stirrer, 30.0 g of this was sufficiently obtained using a zirconia bead of 0.3 mm diameter with a planetary ball mill (P-7 manufactured by Fritsch). Then, the zirconia beads were separated with a sieve to obtain a zinc oxide ultrafine particle dispersion. To 9.0 g of this zinc oxide ultrafine particle dispersion, 5.0 g of ethyl acetate and 6.0 g of the polyester resin (6) are added and stirred to obtain a coating liquid (a-11) (solid content concentration 15% by mass). It was.

(Preparation Example 12)
To 79.87 g of ethyl acetate, 20 g of ultrafine zinc oxide particles and 0.13 g of amine salt (1) of polyester acid resin as a dispersant were added and stirred thoroughly with a stirrer. After sufficiently dispersing with 0.3 mm diameter zirconia beads (Fritsch P-7), the zirconia beads were separated with a sieve to obtain a zinc oxide ultrafine particle dispersion. To 9.0 g of this zinc oxide ultrafine particle dispersion, 5.05 g of ethyl acetate and 5.96 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 66.7 g of ethyl acetate, 20 g of zinc oxide ultrafine particles and 13.3 g of amine salt (1) of a polyester acid resin as a dispersant were added and stirred well with a stirrer. After sufficiently dispersing with 0.3 mm diameter zirconia beads (Fritsch P-7), the zirconia beads were separated with a sieve to obtain a zinc oxide ultrafine particle dispersion. To 9.0 g of this zinc oxide ultrafine particle dispersion, 9.5 g of ethyl acetate and 1.5 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 76 g of ethyl acetate, 20 g of zinc oxide ultrafine particles and 4 g of an amine salt (4) of a polyether phosphate ester resin as a dispersant were added, and after sufficient stirring with a stirrer, 30.0 g of this was transferred to a planetary ball mill ( After fully dispersing using 0.3 mm-diameter zirconia beads by Frichtu P-7), 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, 6.8 g of ethyl acetate and 4.2 g of polyester resin (6) are added and stirred to obtain a coating liquid (a-14) (solid content concentration of 15% by mass). It was.

(Preparation Example 15)
To 66.3 g of distilled water, 30.0 g of zinc oxide ultrafine particles and 3.75 g of sodium polycarboxylate (5) as a dispersant were added, and after sufficient stirring with a stirrer, 30.0 g of this was added to a planetary ball mill ( After fully dispersing using 0.3 mm-diameter zirconia beads by Frichtu P-7), the zirconia beads were separated by sieving to obtain a zinc oxide ultrafine particle aqueous dispersion. To 6.0 g of this zinc oxide ultrafine particle aqueous dispersion, 6.9 g of distilled water and 3.7 g of polyester resin (8) are added and stirred, then 3.4 g of isopropyl alcohol is added and stirred, and the coating liquid (a -15) (solid content concentration 15% by mass).

(Preparation Example 16)
Polyacrylic acid (trade name: Aron A-10H, number average molecular weight 200,000, solid concentration 25% by weight aqueous solution, manufactured by Toagosei Co., Ltd.) and glycerin are 90/10 in mass ratio (solid content ratio). The coating solution (b-1) was prepared by adding 2.55 parts by mass of 3-glycidoxypropyltrimethoxysilane to 100 parts by mass of polyacrylic acid.

<Preparation of gas barrier laminate for thermoforming>
Example 1
Polyester main agent (Mitsui Chemical Polyurethanes, Takelac (registered trademark) A525: solid content concentration 50 parts by mass) and curing agent (Mitsui Chemicals Polyurethanes, Takenate (registered trademark) A52: solids concentration 75 parts by mass) Were dissolved in a solvent (ethyl acetate) so that the mass ratio (main agent / curing agent) was 9/1 to obtain a coating solution for anchor coat layer having a solid content concentration of 5 parts by mass.
The obtained coating solution for anchor coat layer is applied on 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.
On the formed anchor coat layer, the coating liquid (b-1) was applied using a bar coater so that the thickness after drying was 1.0 μm and dried to form a layer.
Next, the coating liquid (a-1) is applied and dried on the layer formed from the coating liquid (b-1) using the bar coater so that the thickness after drying becomes 1.2 μm. To form a layer.
Thus, an anchor coat layer on the polyester film, a layer formed from the coating liquid (b-1) (layer (B)), and a layer formed from the coating liquid (a-1) (layer (A)) However, a gas barrier laminate for thermoforming laminated in this order was obtained.

(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).

(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-9) 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-10) 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-11) 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-12) 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-13) 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-14) was used instead of the coating liquid (a-1).

(Comparative Example 7)
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).

<Evaluation 1: Thermoformability>
(1) Production of laminate sheet:
Using an adhesive, with a small table laminator manufactured by Tester Sangyo Co., Ltd., a gas barrier laminate for thermoforming obtained in each example (Examples 1 to 8, Comparative Examples 1 to 7) and unstretched with a thickness of 600 μm A polypropylene sheet (CPP) was bonded to obtain a laminate sheet having the structure of thermoforming gas barrier laminate / adhesive / CPP. The gas barrier laminate for thermoforming was disposed so that the laminate surface (surface on the gas barrier layer side) was in contact with the adhesive. As the adhesive, a two-pack curable adhesive, Takelac A525 (main agent) / Takenate A52 (hardener) manufactured by Mitsui Chemicals, Inc. was used. The obtained laminate sheet was cured at 40 ° C. for 3 days after bonding.

(2) Production of molded container (molded body) by thermoforming:
The obtained laminate sheet (configuration: 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 / pressure forming machine manufactured by Yanagishita Giken Co., Ltd. A molded container was obtained by thermoforming into a shape of The diameter W of the molded 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 as a heat sterilization treatment using a retort treatment machine (Hisaka Manufacturing Co., Ltd .: RCS-600). With respect to the molded container after the retort treatment, an oxygen transmission rate was measured using an oxygen permeation tester (OXTRAN 2/20, manufactured by Modern Control) with the atmosphere inside and outside the container at a temperature of 20 ° C. and a relative humidity of 50%. The measured value of oxygen permeability one day after the start of the measurement is converted using the values of the oxygen concentration in the atmosphere (20%) and the surface area of the container (0.018 m ² ).
In accordance with K-7126 “Method B (isobaric method)” and ASTM D3985-81, the 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 standard conditions (0 ° C., 1 atm) for defining the volume of oxygen. The lower the oxygen permeability of the molded container, the better the thermoformability. The evaluation results are shown in Table 1.
In Comparative Example 7, the film could not be stretched during thermoforming, and the laminate sheet was broken, so that the oxygen permeability was not measured.

<Evaluation 2: Stability of coating liquid (a)>
The coating liquids (a-1) to (a-15) used for forming the layer (A) in Examples and Comparative Examples were visually observed immediately after the preparation for the precipitation of zinc oxide ultrafine particles. It was evaluated with. The evaluation results are shown in Table 1.
○: No sedimentation.
X: 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 8 had good liquid stability.
Moreover, the molding container which thermoformed the gas barrier property laminated body for thermoforming obtained in Examples 1 to 8 had excellent gas barrier properties. From this, the gas barrier laminate for thermoforming of Examples 1 to 8 is excellent in thermoformability, and when the gas barrier laminate for thermoforming is thermoformed and heat-sterilized, it has excellent gas barrier properties. It was confirmed that a molded body having the above can be obtained.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the gas-barrier laminated body for thermoforming which the molded object obtained by thermoforming and heat-sterilizing has the gas barrier property which was excellent, and a molded object using the same.

1 Base Material 2 Gas Barrier Layer 3 Layer (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 (4)

One or more dispersants selected from amine salts of polyester acid resins, polyether phosphate resins (excluding amine salts), fatty acid esters, ultrafine zinc oxide particles, and polyester resins (however, polyester acids) And organic solvents),
Content of the said zinc oxide ultrafine particle is 20-90 mass% with respect to the total mass of all the solid content in a coating liquid,
The coating liquid whose content of the said dispersing agent is 1-40 mass parts with respect to 100 mass parts of said zinc oxide ultrafine particles. A gas barrier laminate for thermoforming having a substrate and a gas barrier layer formed on the substrate,
The gas barrier layer comprises at least one dispersant selected from amine salts of polyester acid resins, polyether phosphate resins (excluding amine salts), fatty acid esters, zinc oxide ultrafine particles, and polyester resins. A layer (A) containing a resin (excluding a polyester acid resin) and a layer (B) containing a polycarboxylic acid polymer,
Content of the said zinc oxide ultrafine particle is 20-90 mass% with respect to the total mass of the said layer (A),
The gas barrier laminate for thermoforming, wherein the content of the dispersant is 1 to 40 parts by mass with respect to 100 parts by mass of the zinc oxide ultrafine particles.   The gas barrier laminate for thermoforming according to claim 2, wherein the layer (A) is a layer formed from the coating liquid according to claim 1.   The molded object using the gas-barrier laminated body for thermoforming of Claim 2 or 3.

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