JP2009018473A - Manufacturing process of gas-barriering molded laminate and gas-barriering molded laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas-barriering molded laminate which is excellent in a gas barrier property and to provide the manufacturing process of the gas-barriering molded laminate which is excellent in moldability. <P>SOLUTION: The manufacturing process of the gas-barriering molded laminate comprises: a process (A1) of forming a laminate (A1) by laminating a layer (A1) on a base material by applying a coating solution (A) containing a polycarboxylic acid polymer, a hydrolysis condensate of at least one sort of compounds expressed by general formula (1): M<SP>1</SP>(OR<SP>1</SP>)<SB>n</SB>R<SP>2</SP><SB>m-n-t-s</SB>X<SP>1</SP><SB>t</SB>Z<SP>1</SP><SB>s</SB>and a plasticizer; a process (B1) of forming a laminate (B1) by laminating a polyvalent metal compound-containing layer (B1) on the layer (A1) of the laminate (A1); a process (C1) of forming a molded laminate (C1) by stretching the laminate (B1) so that area magnification becomes 1.1 to 100 times; and a process (D1) of bringing a carboxyl group of the polycarboxylic acid polymer contained in the layer (A1) of the molded laminate (C1) into reaction with a polyvalent metal ion originated in the polyvalent metal compound contained in the layer (B1). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

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

  Conventionally, a method for producing a gas barrier film having excellent water resistance is formed by applying a coating liquid containing a polycarboxylic acid polymer and a polyalcohol polymer onto a plastic film and drying it. A stretched laminated film formed by stretching a laminated film having a coated layer is known (see, for example, Patent Document 1 and Patent Document 2). The stretched laminated film is subjected to a heat treatment to form an ester bond between a carboxyl group in the polycarboxylic acid polymer and a hydroxyl group in the polyalcohol polymer. It was a laminated film excellent in water resistance. However, in order to obtain gas barrier properties and water resistance, it is necessary to form a sufficient ester bond by high-temperature and long-time heat treatment, which tends to be inferior in productivity. Further, when the ester bond is not sufficiently formed, the gas barrier property is lowered, and there is still room for improvement.

  Also known is a gas barrier laminate in which a layer containing a polycarboxylic acid and a hydrolysis condensate of a compound containing a metal atom to which at least one characteristic group selected from a halogen atom and an alkoxy group is bonded is formed on a stretched film. (See, for example, Patent Document 3).

However, since the laminate lacks the flexibility (stretchability) of the gas barrier layer, the gas barrier properties deteriorate when the laminate is stretched.
Japanese Patent Laid-Open No. 10-316779 JP 2000-37822 A International Publication No. 05/053954 Pamphlet

  The present invention has been made in view of the above-described problems of the prior art, and a method for producing a gas barrier molded laminate having excellent moldability capable of producing gas barrier molded laminates having various shapes and the production method thereof. It aims at providing the gas barrier property shaping | molding laminated body which is excellent in the gas barrier property obtained.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that the gas barrier molded laminate obtained by the following first to fourth methods for producing a gas barrier molded laminate has excellent gas barrier properties and moldability. As a result, the present invention was completed.

That is, the first method for producing a gas barrier molded laminate of the present invention is as follows.
A coating liquid (A) containing a polycarboxylic acid polymer, a hydrolysis condensate of at least one compound represented by the following general formula (1), and a plasticizer is applied on a substrate. A step (A1) of laminating the layer (A1) to form a laminate (A1);
A step (B1) of laminating a layer (B1) containing a polyvalent metal compound on the layer (A1) of the laminate (A1) to form a laminate (B1);
Stretching the laminate (B1) so that the area magnification is 1.1 to 100 times to form a molded laminate (C1) (C1);
A step of reacting a carboxyl group of the polycarboxylic acid polymer contained in the layer (A1) of the molded laminate (C1) with a polyvalent metal ion derived from the polyvalent metal compound contained in the layer (B1) ( D1).

The method for producing the second gas barrier molded laminate of the present invention comprises:
A coating liquid (A) containing a polycarboxylic acid polymer, a hydrolysis condensate of at least one compound represented by the following general formula (1), and a plasticizer is applied on a substrate. A step (A2) of laminating the layer (A2) to form a laminate (A2);
Stretching the laminate (A2) to an area magnification of 1.1 to 100 times to form a molded laminate (C2) (C2);
A step (B2) of laminating a layer (B2) containing a polyvalent metal compound on the layer (A2) of the molded laminate (C2) to form a molded laminate (B2);
A step of reacting a carboxyl group of the polycarboxylic acid polymer contained in the layer (A2) of the molded laminate (B2) with a polyvalent metal ion derived from the polyvalent metal compound contained in the layer (B2) ( D2).

The method for producing the third gas barrier molded laminate of the present invention comprises:
A coating liquid (A) containing a polycarboxylic acid polymer, a hydrolysis condensate of at least one compound represented by the following general formula (1), and a plasticizer is applied on a substrate. A step (A3) of laminating the layer (A3) to form a laminate (A3);
Stretching the laminate (A3) so that the area magnification is 1.1 to 100 times to form a molded laminate (C3) (C3);
A step (D3) of reacting a carboxyl group of the polycarboxylic acid polymer contained in the layer (A3) of the molded laminate (C3) with a polyvalent metal ion derived from the polyvalent metal compound. Features.

The method for producing the fourth gas barrier molded laminate of the present invention comprises:
A step (B4) of laminating a layer (B4) containing a polyvalent metal compound on the substrate to form a laminate (B4);
A coating comprising a polycarboxylic acid polymer, a hydrolysis condensate of at least one compound represented by the following general formula (1), and a plasticizer on the layer (B4) of the laminate (B4). A step (A4) of applying the liquid (A) to laminate the layer (A4) to form a laminate (A4);
Stretching the laminate (A4) to an area magnification of 1.1 to 100 times to form a molded laminate (C4) (C4);
A step of reacting a carboxyl group of the polycarboxylic acid polymer contained in the layer (A4) of the molded laminate (C4) with a polyvalent metal ion derived from the polyvalent metal compound contained in the layer (B4) ( D4).

M ¹ (OR ¹ ) _n R ² _mnts X ¹ _t Z ¹ _s (1)
(In the general formula (1), M ¹ is Si, Al, Ti or Zr, R ¹ is an alkyl group having 1 to 6 carbon atoms, R ² is an alkyl group having 1 to 10 carbon atoms, an aralkyl group, An aryl group,
An alkenyl group, an alkyl group substituted with an acryloxy group, or an alkyl group substituted with a methacryloxy group, X ¹ is a halogen atom, Z ¹ is a glycidyloxy group, an epoxy group, a mercapto group, a hydroxyl group, an amino group, Or it is an organic group containing an isocyanate group. M represents the valence of M ¹ , n represents an integer of 0 to m, s is 0 or 1,
t represents an integer of 0 to m. Further, n + t ≠ 0, and 1 ≦ n + t + s ≦ m.
When a plurality of R ¹ , R ² and X ¹ are present, each R ¹ , R ² and X ¹ may be the same or different. )
The step (D1) is preferably a step of applying at least one treatment selected from the group consisting of a humidity control treatment, a boil treatment, and a retort treatment to the molded laminate (C1).

It is preferable that the said process (D2) is a process of performing at least 1 sort (s) of processing selected from the group which consists of a humidity control process, a boil process, and a retort process to a shaping | molding laminated body (B2).
The step (D3) includes a step of immersing the molded laminate (C3) in a liquid containing a polyvalent metal compound and drying, and a liquid containing the polyvalent metal compound in the layer (A3) of the molded laminate (C3). At least one process selected from the group consisting of spraying and drying is preferred.

The step (D4) is preferably a step of applying to the molded laminate (C4) at least one treatment selected from the group consisting of a humidity control treatment, a boil treatment, and a retort treatment.
The weight ratio of the polycarboxylic acid polymer contained in the coating liquid (A) to the plasticizer is preferably 99.5: 0.5 to 70:30.

  The weight ratio of the polycarboxylic acid polymer contained in the coating liquid (A) to the hydrolysis condensate of at least one compound represented by the general formula (1) is 99.5: 0.5 to It is preferably 40:60.

  The polycarboxylic acid polymer contained in the coating liquid (A) is a structural unit derived from at least one polymerizable monomer selected from acrylic acid, maleic acid, methacrylic acid, and itaconic acid. A (co) polymer containing or a mixture of the (co) polymers is preferred.

  The plasticizer contained in the coating liquid (A) is preferably at least one plasticizer selected from the group consisting of polyethylene glycol, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, starch and glycerin.

The polyvalent metal compound contained in the layer (B1), (B2) or (B4) is preferably a calcium compound or a zinc compound.
In the step (D3), the polyvalent metal compound is preferably a calcium compound or a zinc compound.

The shape of the gas barrier molded laminate is preferably in any form selected from the group consisting of a film, a sheet, a bottle, a cup, a tray, a container, a tank and a tire.
Further, the present invention includes a gas barrier molded laminate produced by the above method for producing a gas barrier molded laminate.

  Since the method for producing a gas barrier molded laminate of the present invention is excellent in moldability, various shapes of gas barrier molded laminates can be produced, and the resulting gas barrier molded laminate is excellent in gas barrier properties.

Hereinafter, the present invention will be specifically described.
Examples of the method for producing the gas barrier molded laminate of the present invention include the following first to fourth methods for producing a gas barrier molded laminate.

In addition, the manufacturing method of the 1st-4th gas-barrier shaping | molding laminated body is also described as the 1st-4th manufacturing method, respectively.
That is, in the first method for producing a gas barrier molded laminate of the present invention, a hydrolytic condensation of a polycarboxylic acid polymer and at least one compound represented by the following general formula (1) on a substrate. A layer (A1) is formed by applying a coating liquid (A) containing a product and a plasticizer to form a laminate (A1), and the layer (A1) of the laminate (A1) ) A layer (B1) containing a polyvalent metal compound is laminated thereon to form a laminate (B1), and the laminate (B1) has an area magnification of 1.1 to 100 times. Stretching (C1) to form the molded laminate (C1), the carboxyl group of the polycarboxylic acid polymer contained in the layer (A1) of the molded laminate (C1), and the layer (B1) A step (D1) of reacting a polyvalent metal ion derived from a polyvalent metal compound contained in Characterized in that it has.

  In the method for producing a second gas barrier molded laminate of the present invention, a polycarboxylic acid polymer and a hydrolysis condensate of at least one compound represented by the following general formula (1) are formed on a base material. The step (A2) of forming the laminate (A2) by applying the coating liquid (A) containing the plasticizer and laminating the layer (A2); and the area magnification of the laminate (A2) is 1. Stretching to 1 to 100 times to form a molded laminate (C2) (C2) and a layer (B2) containing a polyvalent metal compound on the layer (A) of the molded laminate (C2) ) To form the molded laminate (B2), the carboxyl group of the polycarboxylic acid polymer contained in the layer (A2) of the molded laminate (B2), and the layer (B2) And a step (D2) of reacting with a polyvalent metal ion derived from a polyvalent metal compound contained in And wherein the Rukoto.

  According to the third method for producing a gas barrier molding laminate of the present invention, a polycarboxylic acid polymer and a hydrolysis condensate of at least one compound represented by the following general formula (1) are formed on a substrate. The layer (A3) is formed by applying a coating liquid (A) containing a plasticizer and laminating the layer (A3), and the laminate (A3) has an area magnification of 1. The step (C3) of forming the molded laminate (C3) by stretching to 1 to 100 times, and the carboxyl group of the polycarboxylic acid polymer contained in the layer (A3) of the molded laminate (C3) And a step (D3) of reacting a polyvalent metal ion derived from the polyvalent metal compound.

  The method for producing a fourth gas barrier molded laminate of the present invention includes a step (B4) of laminating a layer (B4) containing a polyvalent metal compound on a substrate to form a laminate (B4), A coating liquid comprising a polycarboxylic acid polymer, a hydrolysis condensate of at least one compound represented by the following general formula (1), and a plasticizer on the layer (B4) of the laminate (B4). (A) is applied, the layer (A4) is laminated, and the layered body (A4) is formed (A4), and the layered body (A4) has an area magnification of 1.1 to 100 times. Stretched to form the molded laminate (C4) (C4), the carboxyl group of the polycarboxylic acid polymer contained in the layer (A4) of the molded laminate (C4), and included in the layer (B4) And a step (D4) of reacting with a polyvalent metal ion derived from the polyvalent metal compound to be produced. The features.

M ¹ (OR ¹ ) _n R ² _mnts X ¹ _t Z ¹ _s (1)
(In the general formula (1), M ¹ is Si, Al, Ti or Zr, R ¹ is an alkyl group having 1 to 6 carbon atoms, R ² is an alkyl group having 1 to 10 carbon atoms, an aralkyl group, An aryl group,
An alkenyl group, an alkyl group substituted with an acryloxy group, or an alkyl group substituted with a methacryloxy group, X ¹ is a halogen atom, Z ¹ is a glycidyloxy group, an epoxy group, a mercapto group, a hydroxyl group, an amino group, Or it is an organic group containing an isocyanate group. M represents the valence of M ¹ , n represents an integer of 0 to m, s is 0 or 1,
t represents an integer of 0 to m. Further, n + t ≠ 0, and 1 ≦ n + t + s ≦ m.
When a plurality of R ¹ , R ² and X ¹ are present, each R ¹ , R ² and X ¹ may be the same or different. )
Hereinafter, each component used in the present invention (base material, polycarboxylic acid polymer, hydrolysis condensate, etc.),
The coating liquid and the like will be described in detail, and then the method for producing a gas barrier molded laminate and the gas barrier molded laminate will be described in detail.

<Base material>
The substrate used in the present invention is made of plastics or rubber.
As a base material, a film or sheet usually formed from plastics or rubber is used. There is no limitation in particular as a shaping | molding method of a base material, For example, what was shape | molded by methods, such as extrusion molding, injection molding, blow molding, can be used.

Further, the substrate may be composed of a single layer, or may be composed of a plurality of layers by lamination or the like.
The base material used by this invention is for laminating | stacking a layer (B4) in a layer (A1)-layer (A3) in the process (A1)-process (A3) mentioned later, and a process (B4).

Examples of the material of the base material made of plastics used in the present invention include polyolefin polymers such as low density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, poly-4-methylpentene, cyclic polyolefin, and the like. Copolymers, and acid-modified products thereof; polyvinyl acetate, ethylene-vinyl acetate copolymer, saponified ethylene-vinyl acetate copolymer, polyvinyl alcohol, and other vinyl acetate copolymers; polyethylene terephthalate, polybutylene Polyester polymers such as terephthalate, polyethylene naphthalate, polyε-caprolactone, polyhydroxybutyrate and their copolymers; nylon 6, nylon 66, nylon 12, nylon 6,66 copolymer, nylon 6,12 Polymer, metaxylene azimuth Polyamide polymers such as Pamide / Nylon 6 copolymer and copolymers thereof; Polyether polymers such as polyethersulfone, polyphenylene sulfide, polyphenylene oxide; polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyfluoride Chlorinated and fluorinated polymers such as vinylidene and their copolymers; acrylic polymers such as polymethyl acrylate, polyethyl acrylate, polymethyl methacrylate, polyethyl methacrylate, polyacrylonitrile, and their copolymers; polystyrene Styrene polymers such as ABS resins and their copolymers; polyimide polymers and their copolymers; alkyd resins, melamine resins, acrylic resins, nitrified cotton, urethane resins, unsaturated polyester resins, phenol resins, amino acids Tree , Fluororesin, resin such as epoxy resin used in the paint; cellulose, starch, pullulan, chitin, chitosan, glucomannan, agarose, natural polymer compounds such as gelatin.

  As the material, polyethylene terephthalate, polypropylene, linear low density polyethylene, nylon 6, nylon 6,66 copolymer, and polystyrene are preferable in terms of gas barrier properties and film strength.

  Examples of the material of the base material made of rubber used in the present invention include natural rubber, isoprene rubber, styrene-butadiene rubber, butadiene rubber, acrylonitrile-butadiene rubber, butyl rubber, ethylene-propylene rubber, chlorobrene rubber, and acrylic rubber. Chlorosulfonated polyethylene rubber, hydrin rubber, urethane rubber, polysulfide rubber, silicone rubber, fluorine rubber and the like.

The thickness of the base material made of plastics or rubber after stretching (the thickness of the base material after stretching in the step (C1) to the step (C4)) varies depending on the use and the like. 5 μm to 5 cm. When the shape of the gas barrier molded laminate obtained by the production method of the present invention is a film or sheet, it is preferably 5 to 800 μm, more preferably 10 to 500 μm. When the shape of the gas barrier molded laminate is a bottle, cup, tray, container, or tank, 100 μm to 1 cm is preferable, and 150 μm to 80 mm is more preferable. Moreover, when the shape of a gas-barrier molded laminated body is a tire, 1-5 cm is preferable. When the thickness of the substrate is within the above range, the workability and productivity in each application are excellent.

  From the viewpoint of improving the peel strength between the substrate and the layer (A1) to the layer (A3) or the layer (B4), the gas barrier molded laminate obtained by the method for producing a gas barrier molded laminate of the present invention. The surface of the substrate may be subjected to surface activation treatment by corona treatment, flame treatment, plasma treatment or the like, and further, a substrate having an anchor coat layer on the surface may be used.

  As the resin used for such an anchor coat layer, for example, alkyd resin, melamine resin, acrylic resin, nitrified cotton, urethane resin, polyester resin, phenol resin, amino resin, fluorine resin, epoxy resin can be used. Resins, polyester resins, acrylic resins and epoxy resins are preferred.

  In particular, a urethane resin is preferable, and the polyol constituting the urethane resin is preferably a polyester-based polyol. Examples of the polyester-based polyol include a polyester-based polyol obtained by reacting a polyvalent carboxylic acid with a glycol. It is done.

  Examples of the polyisocyanate constituting the urethane resin include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, Examples include xylylene diisocyanate and isophorone diisocyanate.

  When using the base material provided with the anchor coat layer, the thickness of the anchor coat layer is preferably 0.01 to 1 μm, and preferably 0.05 to 1 μm from the viewpoint of adhesion and appearance. More preferred.

  The base material made of plastics used in the present invention may be either unstretched or stretched. For example, a 120 μm-thick polyethylene terephthalate film formed by melt extrusion using a T-die method as a base material and subjected to longitudinal stretching at a stretching ratio of about 3 times at a temperature of about 90 ° C. is used as the base material. Also good.

(Polycarboxylic acid polymer)
The coating liquid (A) used in the present invention contains a polycarboxylic acid polymer. The polycarboxylic acid polymer is a polymer obtained by polymerizing a carboxylic acid polymerizable monomer, and is a polymer having two or more carboxyl groups in the molecule. Examples of such polycarboxylic acid-based polymers include (co) polymers of ethylenically unsaturated carboxylic acids; copolymers of ethylenically unsaturated carboxylic acids and other ethylenically unsaturated monomers; alginic acid , Acidic polysaccharides having a carboxyl group in the molecule such as carboxymethylcellulose and pectin. These polycarboxylic acid polymers may be used alone or in combination of two or more.

  Examples of such ethylenically unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid. Furthermore, as the ethylenically unsaturated monomer copolymerizable with these ethylenically unsaturated carboxylic acids, for example, saturated carboxylic acid vinyl esters such as ethylene, propylene, vinyl acetate, alkyl acrylates, alkyl methacrylates, Examples thereof include alkyl itaconates, vinyl chloride, vinylidene chloride, styrene, acrylamide, and acrylonitrile.

  Among such polycarboxylic acid polymers, from the viewpoint of gas barrier properties of the resulting gas barrier molded laminate, the polycarboxylic acid polymer is acrylic acid, maleic acid, methacrylic acid, itaconic acid, fumaric acid, and It is preferably a (co) polymer containing a structural unit derived from at least one polymerizable monomer selected from crotonic acid, or a mixture of the (co) polymer, acrylic acid, maleic acid , A (co) polymer containing a structural unit derived from at least one polymerizable monomer selected from methacrylic acid and itaconic acid, or a mixture of the (co) polymers. . In the (co) polymer, the structural unit derived from the polymerizable monomer is preferably 80 mol% or more, more preferably 90 mol% or more (however, all the structural units are 100 mol%). To do). When a structural unit other than the structural unit derived from the polymerizable monomer is included, the other structural unit includes, for example, the above-mentioned ethylenically unsaturated monomer (however, the ethylenically unsaturated carboxylic acid). Excluding acids).

  The polycarboxylic acid polymer used in the present invention usually has a number average molecular weight in the range of 2,000 to 10,000,000. When the number average molecular weight is less than 2,000, the obtained gas barrier molded laminate cannot achieve sufficient water resistance, and the gas barrier property and transparency may deteriorate due to moisture, or whitening may occur. On the other hand, when the number average molecular weight exceeds 10,000,000, the coating property is impaired because the viscosity is high. Furthermore, from the viewpoint of water resistance of the obtained gas barrier molded laminate, the number average molecular weight of such a polycarboxylic acid polymer is preferably in the range of 5,000 to 1,000,000.

In addition, as a polycarboxylic acid-type polymer used for this invention, it may be used individually by 1 type, and 2 or more types may be mixed and used for it.
(Hydrolysis condensate)
The coating liquid (A) contains a hydrolysis condensate of at least one compound represented by the following general formula (1). The hydrolysis-condensation product of at least one compound represented by the following general formula (1) is subjected to hydrolysis and condensation reaction of at least one compound represented by the general formula (1) using a sol-gel method. Can be obtained.

In the present specification, the “hydrolysis condensate of at least one compound represented by the general formula (1)” is also simply referred to as “hydrolysis condensate”.
The hydrolysis condensate includes a partial hydrolysis condensate and a complete hydrolysis condensate of at least one compound represented by the general formula (1), which may be a mixture of these, A partial hydrolyzate or a complete hydrolyzate of at least one compound represented by (1) may be contained.

  As a method for producing the hydrolysis-condensation product using the sol-gel method, there is a method of performing hydrolysis and subsequent condensation by adding water to at least one compound represented by the following general formula (1). Can be mentioned. An acid may be added to accelerate the hydrolysis reaction. Moreover, in order to improve the solubility of a hydrolysis-condensation product, you may add alcohol.

  Moreover, you may manufacture the hydrolysis-condensation product used for this invention by hydrolyzing and condensing at least 1 type of compound represented by General formula (1) in multiple steps. That is, after making at least one compound represented by the general formula (1) into a condensate of about 2 to 10 mer, the condensate of about 2 to 10 mer is further hydrolyzed and condensed to hydrolyze. You may manufacture as a decomposition condensate.

M ¹ (OR ¹ ) _n R ² _mnts X ¹ _t Z ¹ _s (1)
(In the general formula (1), M ¹ is Si, Al, Ti or Zr, and R ¹ has 1 to 6 carbon atoms.
R ² is an alkyl group having 1 to 10 carbon atoms, an aralkyl group, an aryl group,
An alkenyl group, an alkyl group substituted with an acryloxy group, or an alkyl group substituted with a methacryloxy group, X ¹ is a halogen atom, Z ¹ is a glycidyloxy group, an epoxy group, a mercapto group, a hydroxyl group, an amino group, Or it is an organic group containing an isocyanate group. M represents the valence of M ¹ , n represents an integer of 0 to m, s is 0 or 1,
t represents an integer of 0 to m. Further, n + t ≠ 0, and 1 ≦ n + t + s ≦ m.
When a plurality of R ¹ , R ² and X ¹ are present, each R ¹ , R ² and X ¹ may be the same or different. )
The at least one compound represented by the general formula (1) includes at least one compound represented by the following general formula (2) and / or at least one compound represented by the general formula (3). It is preferable that there is, and a mixture thereof may be used.

M ² (OR ³ ) _k X ² _l Z ² _gkl (2)
(In the general formula (2), M ² is Si, Al, Ti or Zr, R ³ is an alkyl group having 1 to 6 carbon atoms, X ² is a halogen atom, Z ² is a glycidyloxy group, An organic group substituted with an epoxy group, a mercapto group, a hydroxyl group, an amino group, or an isocyanate group.
G represents the valence of M ² , k represents an integer of 0 to (g-1), and l represents an integer of 0 to (g-1). Further, 1 ≦ k + l ≦ (g−1).
When a plurality of R ³ , X ² and Z ² are present, each R ³ , X ² and Z ² may be the same or different. )
M ³ (OR ⁴ ) _p R ⁵ _jpq X ³ _q (3)
(In the general formula (3), M ³ is Si, Al, Ti or Zr, R ⁴ is an alkyl group having 1 to 6 carbon atoms, R ⁵ is an alkyl group, an aralkyl group having 1 to 10 carbon atoms, An aryl group,
An alkyl group substituted with an alkenyl group, an acryloxy group, or an alkyl group substituted with a methacryloxy group, and X ³ is a halogen atom.
J represents the valence of M ³ , p represents an integer of 0 to j, q represents an integer of 0 to j, and 1 ≦ p + q ≦ j.
When a plurality of R ⁴ , R ⁵ and X ³ are present, each R ⁴ , R ⁵ and X ³ may be the same or different. )
Specific examples of the compound represented by the general formula (2) include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-chloropropyltrimethoxysilane, and γ-chloropropyltriethoxy. Examples include silane, γ-aminopropyltrimethoxysilane, and γ-aminopropyltriethoxysilane, and γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropyltriethoxysilane are preferable.

  Specific examples of the compound represented by the general formula (3) include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, methacryloxypropyltri Methoxysilane, methacryloxypropyltriethoxysilane, acryloxypropyltrimethoxysilane, and acryloxypropyltriethoxysilane are preferred.

  The coating liquid (A) contains a hydrolysis condensate of at least one compound represented by the general formula (1), preferably at least one compound represented by the general formula (2) and / or It includes a hydrolysis condensate of at least one compound represented by formula (3).

This hydrolysis condensate is represented by at least one compound represented by general formula (1), preferably at least one compound represented by general formula (2) and / or represented by general formula (3). An alkoxy group (OR ¹ , OR ³ , OR ⁴ ) of at least one compound and a halogen atom (
X ¹ , X ² , X ³ ) are at least partially substituted with a hydroxyl group to form a hydrolyzate, and the hydrolyzate further condenses to allow metal atoms (M ¹ , M ² , M ³ ) to pass through oxygen. To form a bound compound. By repeating this condensation, a hydrolysis condensate is obtained.

  The hydrolyzed condensate used in the present invention is a hydrolyzed condensate of at least one compound represented by general formula (2), or a hydrolytic condensate of at least one compound represented by general formula (3). Or at least one compound represented by the general formula (2) and at least one compound represented by the general formula (3) are preferred.

  The amount of the hydrolysis condensate of at least one compound represented by the general formula (1) contained in the coating liquid (A) is a polycarboxylic acid type from the viewpoint of gas barrier properties and water resistance of the gas barrier molded laminate. Weight ratio of polymer to hydrolysis condensate of at least one compound represented by general formula (1) (polycarboxylic acid polymer: hydrolysis of at least one compound represented by general formula (1) The decomposition condensate) is preferably 99.9: 0.1 to 30:70, more preferably 99.5: 0.5 to 40:60.

  In particular, when the weight ratio of the polycarboxylic acid polymer and the hydrolysis condensate of at least one compound represented by the general formula (1) is in the range of 70:30 to 30:70, As the compound represented by the general formula (1), a mixture of the compounds represented by the general formula (2) and the general formula (3) can be suitably used. When the compound represented by the general formula (2) and the general formula (3) is used as the compound represented by the general formula (1), the laminate ( A1) to layer (A4) layer (A1) to layer (A4) tend to have excellent flexibility, and when the proportion of the compound represented by formula (3) is large, the resulting gas barrier molding There exists a tendency for the gas barrier property of a laminated body to be excellent. The compound represented by the general formula (1) may not be a mixture of the compounds represented by the general formula (2) and the general formula (3), but the general formula (2) and the general formula (3). When a mixture of compounds represented by formula (2) is used, the molar ratio of the compound represented by formula (2) to the compound represented by formula (3) (compound represented by formula (2): formula The compound represented by (3) is preferably in the range of 0.1: 99.9 to 40:60, and more preferably in the range of 1:99 to 20:80.

(Plasticizer)
The coating liquid (A) contains a plasticizer. The plasticizer is preferably a compound having a low melting point and compatible with a polycarboxylic acid polymer. Specific examples include ethylene glycol, trimethylene glycol, propylene glycol, tetramethylene glycol, and 1,3-butane. Diol, 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, Examples thereof include lactic acid, fatty acid, starch, and phthalate ester. These may be used in a mixture as required.

  Among these, those having a hydroxyl group are preferred, and polyethylene glycol, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, starch, and glycerin are preferred from the viewpoints of stretchability and gas barrier properties.

  The plasticizer contained in the coating liquid (A) is usually 99.5: 0.5 to 70:30 in the weight ratio of the polycarboxylic acid polymer to the plasticizer (polycarboxylic acid polymer: plasticizer). It is preferable that it is 99: 1-80: 20.

When there are few plasticizers than the said range, it exists in the tendency for extending | stretching and a moldability of the layer (A1)-layer (A4) which a laminated body (A1)-laminated body (A4) has. On the other hand, when there are more plasticizers than the said range, there exists a tendency for gas barrier property to be inferior.

(Additive)
The coating liquid (A) may contain various additives as other components. Examples of the additive include a resin, a dispersant, a surfactant, a softening agent, a stabilizer, an antiblocking agent, a film forming agent, an adhesive, an oxygen absorbent, and an inorganic salt.

  When the coating liquid (A) contains an additive, the weight ratio of the polycarboxylic acid polymer to the additive (polycarboxylic acid polymer: additive) is usually 99.9: 0. It is the range of 1-70: 30, and it is preferable that it is 98: 2-80: 20.

  As the inorganic salt, for example, sodium hypophosphite, sodium hydroxide, sodium sulfite, and calcium hypophosphite are preferably used from the viewpoint of solubility. Since these inorganic salts have a catalytic action for the esterification reaction, when a resin having a hydroxyl group is used as a plasticizer, it can be added to a polycarboxylic acid polymer when heat-fixed. Ester bonds with the plasticizer are easily formed.

  When the inorganic salt is used, the content of the inorganic salt in the coating liquid (A) is such that the carboxyl group of the polycarboxylic acid polymer contained in the coating liquid (A) is from the viewpoint of gas barrier properties and film-forming properties of the coating layer. In contrast, it is preferably 0.05 chemical equivalent or less, and more preferably 0.01 chemical equivalent or less.

<Coating solution (A)>
Steps (A1) to (A3) in the method for producing the first to third gas barrier molded laminates of the present invention are represented by a polycarboxylic acid polymer and the general formula (1) on a substrate. The layer (A1) to the layer (A3) are laminated by applying the coating liquid (A) containing the hydrolyzed condensate of at least one compound and a plasticizer, and the layered body (A1) to the layered body This is a step of forming (A3).

  Moreover, the process (A4) in the manufacturing method of the 4th gas-barrier shaping | molding laminated body of this invention is a polycarboxylic acid type polymer and the said General formula (1) on the layer (B4) of a laminated body (B4). A coating solution (A) containing a hydrolysis condensate of at least one compound represented by formula (A) and a plasticizer is applied to form a laminate (A4) by laminating the layer (A4). .

  The coating liquid (A) is a coating liquid containing the polycarboxylic acid polymer, a hydrolysis condensate of the compound represented by the general formula (1), and a plasticizer. If necessary, additives and the like May be included.

  The hydrolysis condensate contained in the coating liquid (A) includes a partial hydrolyzate, complete hydrolyzate, partial hydrolyzate condensate, complete hydrolyzate of at least one compound represented by the general formula (1). A decomposition condensate is included.

  The solvent used for the coating liquid (A) is not particularly limited, except that water is required in the hydrolysis reaction of the compound represented by the general formula (1). Water, water and an organic solvent However, water is most preferable from the viewpoint of the solubility of the polycarboxylic acid polymer. An organic solvent such as alcohol is preferable in terms of improving the solubility of the compound represented by the general formula (1) and the coating property of the coating liquid (A). Furthermore, an acid may be added to accelerate the hydrolysis reaction of the compound represented by the general formula (1).

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.

  Moreover, as a mixed solvent of water and an organic solvent, the mixed solvent using water and the organic solvent mentioned above is preferable. As the mixed solvent, water is usually present in an amount of 20 to 95% by weight, and the organic solvent is present in an amount of 80 to 5% by weight (however, the total of water and the organic solvent is 100% by weight). And).

  In the coating liquid (A), from the viewpoints of gas barrier properties and coating properties, the content of the polycarboxylic acid polymer, hydrolysis condensate, plasticizer and additive in the coating liquid (A) (solid %) Is preferably 1 to 50% by weight, more preferably 1 to 30% by weight and even more preferably 2 to 20% by weight based on the total weight of the coating liquid (A).

(Polyvalent metal compound)
In the first to fourth methods for producing a gas barrier molding laminate of the present invention, the carboxyl group of the polycarboxylic acid polymer contained in the layers (A1) to (A4) and a polyvalent metal compound are used. Processes (D1) to (D4) for reacting with valent metal ions are included.

  The polyvalent metal compound used in the present invention is a polyvalent metal compound having a metal ion valence of 2 or more. Examples of the polyvalent metal contained in the polyvalent metal compound include alkaline earth metals such as beryllium, magnesium and calcium; transition metals such as titanium, zirconium, chromium, manganese, iron, cobalt, nickel, copper and zinc; aluminum In particular, calcium or zinc is preferable from the viewpoint of transparency and gas barrier properties. Examples of the polyvalent metal compound include simple substances, oxides, hydroxides, carbonates, organic acid salts, or inorganic acid salts of the polyvalent metals, ammonium complexes of the polyvalent metals, or secondary to quaternary amine complexes. Or carbonates or organic acid salts thereof.

  These polyvalent metal compounds are suitably used depending on the aspects of the steps (D1) to (D4). For example, the step (D3) is a step of immersing the molded laminate (C3) in a liquid containing a polyvalent metal compound and drying, and when the liquid is an aqueous solution, solubility in water and gas barrier properties. From this point of view, it is preferable to use an organic acid salt or inorganic acid salt of calcium or zinc as the polyvalent metal compound, and it is particularly preferable to use an acetate, lactate or chloride of calcium or zinc. In this case, the content of the polyvalent metal compound in the aqueous solution containing the polyvalent metal ion may be 0.5 to 50% by weight when the total weight of the aqueous solution containing the polyvalent metal ion is 100% by weight. Preferably, it is 1 to 40% by weight.

  For example, when the step (D1) is a step of subjecting the molded laminate (C1) to humidity control, boil treatment, or retort processing, or the step (D2) is a humidity control treatment, boil treatment or In the case of a retort treatment step, a polyvalent metal such as an alkaline earth metal, cobalt, nickel, copper, zinc and aluminum is used as the polyvalent metal compound from the viewpoint of gas barrier properties of the resulting gas barrier molded laminate. It is preferable to use oxides, hydroxides, and carbonates of these, and zinc oxide, calcium hydroxide, and calcium carbonate are particularly preferable. In this case, the form of these polyvalent metal compounds may be particulate or non-particulate, but is preferably particulate from the viewpoint of gas barrier properties.

  When forming the layer (B1) or layer (B2) containing a polyvalent metal compound, the coating liquid (B) containing the polyvalent metal compound is applied on the layer (A1) or layer (A2). When the layer (B4) containing a polyvalent metal compound can be formed, the coating liquid (B) containing the polyvalent metal compound can be formed on the substrate by a vapor deposition method. It can also be formed directly using Although a well-known method is used for a vapor deposition method, for example, a physical vapor deposition method and a chemical vapor deposition method are mentioned. The physical vapor deposition method includes a vacuum vapor deposition method, a sputtering method, an ion plating method, and the like, and the chemical vapor deposition method includes a plasma CVD method, a laser CVD method, and the like. Below, the case where it coats on a layer (A1), a layer (A2), and a substrate using a coating liquid (B) is described.

(Coating solution (B))
In the present invention, the layer (B1), the layer (B2) or the layer (B4) containing the polyvalent metal compound is formed on the layer (A1), the layer (A2) or the substrate by vapor deposition of the polyvalent metal compound. However, in terms of productivity, the step (B1), the step (B2) or the step (B4) may be performed by applying the coating liquid (B) containing the polyvalent metal compound to the layer (A1), the layer (A2), or It is preferable to form the layer (B1), the layer (B2) or the layer (B4) by coating on the substrate.

  When the layer (B1), the layer (B2) or the layer (B4) is formed by applying the coating liquid (B), the coating liquid (B) is a coating liquid containing the polyvalent metal compound, and various additives, etc. May be included.

As additives, resins, dispersants, surfactants, softeners, stabilizers, film forming agents, thickeners, and the like can be used.
In the coating liquid (B), it is preferable to mix and use a resin that is soluble or dispersible in the solvent used for the purpose of improving the coating property and film forming property. Examples of such resins include alkyd resins, melamine resins, acrylic resins, urethane resins, polyester resins, phenol resins, amino resins, fluororesins, and epoxy resins.

The coating liquid (B) is preferably mixed with a dispersant that is soluble or dispersible in the solvent used for the purpose of improving the dispersibility of the polyvalent metal compound.
Examples of the solvent used for the coating liquid (B) include water, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, n-pentyl alcohol, dimethyl sulfoxide, dimethylformamide, and dimethylacetamide. , Toluene, hexane, heptane, cyclohexane, acetone, methyl ethyl ketone, diethyl ether, dioxane, tetrahydrofuran, ethyl acetate, butyl acetate. Among these, methyl alcohol, ethyl alcohol, isopropyl alcohol, toluene, and ethyl acetate are preferable from the viewpoint of coatability, and methyl alcohol, ethyl alcohol, isopropyl alcohol, and water are preferable from the viewpoint of productivity.

These solvents may be used alone or in combination of two or more.
The content of the polyvalent metal compound contained in the coating liquid (B) used in the present invention is:
From the viewpoint of gas barrier properties, it is preferably in the range of 0.1 to 50% by weight.

  The method for applying the coating liquid (B) to form the layer (B1), the layer (B2) or the layer (B4) is not particularly limited, but a dipping method, a spray coating method and a coating method using a coater Is mentioned. Examples of coaters include air knife coaters, direct gravure coaters, gravure offsets, arc gravure coaters, top feed reverse coaters, bottom feed reverse coaters, and reverse roll coaters such as nozzle feed reverse coaters, lip coaters, bar coaters, and bar reversers. Examples of the method include coating using a coater and a die coater.

The method for drying the coating liquid (B) is not particularly limited as long as the solvent contained in the coating liquid (B) can be removed. However, the coating liquid (B) is dried by an air drying method or an oven set at a predetermined temperature. Way, arch dryer, floating dryer,
Examples thereof include a method using a dryer such as a drum dryer or an infrared dryer. The drying conditions can be appropriately selected depending on the solvent, the drying method and the apparatus, but are usually in the range of 40 to 250 ° C. and 0.5 seconds to 10 minutes.

<Method for producing gas barrier molded laminate>
Examples of the method for producing the gas barrier molded laminate of the present invention include the first to fourth production methods described above. Each will be described in detail below.

[Production Method of First Gas Barrier Molded Laminate]
The first gas barrier molded laminate production method includes a step (A1) of forming the laminate (A1) by coating the coating liquid (A) on the substrate and laminating the layer (A1). The step (B1) of laminating a layer (B1) containing a polyvalent metal compound on the layer (A1) of the laminate (A1) to form the laminate (B1), and the laminate (B1) The step (C1) of forming the molded laminate (C1) by stretching so that the area magnification is 1.1 to 100 times, and the polycarboxylic acid type contained in the layer (A1) of the molded laminate (C1) It has the process (D1) which makes the carboxyl group of a polymer react with the polyvalent metal ion derived from the polyvalent metal compound contained in a layer (B1). Hereinafter, each step will be described.

(Process (A1))
The step (A1) is a step of forming the layered product (A1) by coating the coating liquid (A) on the substrate and laminating the layer (A1).

  The layer (A1) is usually formed by applying the coating liquid (A) on a substrate and drying it. Although there is no limitation in particular as a method of coating a coating liquid (A) on a base material, The method of coating using a dipping method, spray application, a coater, and a printing machine is mentioned. Examples of coaters, types of printing machines, and coating methods include reverse roll coaters such as air knife coaters, direct gravure coaters, gravure offsets, arc gravure coaters, top feed reverse coaters, bottom feed reverse coaters, and nozzle feed reverse coaters; Examples of the coating method include a lip coater, a bar coater, a bar reverse coater, and a die coater.

  The method of drying the coating liquid (A) is not particularly limited, but is a method of natural drying, a method of drying in an oven set at a predetermined temperature, a dryer attached to a coater, such as an arch dryer, a floating dryer, The method using a drum dryer, an infrared dryer, etc. can be mentioned.

  Further, the drying condition is a condition under which the solvent contained in the coating liquid (A) is removed. Specifically, the drying temperature is preferably 50 to 160 ° C, more preferably 60 to 140 ° C, and particularly preferably 70 to 120 ° C. The drying time is preferably 0.5 seconds to 10 minutes, more preferably 1 second to 5 minutes, and particularly preferably 1 second to 2 minutes.

  In the step (A1), the thickness of the layer (A1) formed from the coating liquid (A) is usually 0.001 to 100 μm, preferably 0.01 to 30 μm, more preferably 0.05. 10 μm.

In addition, as a base material which coats a coating liquid (A) at a process (A1), an unstretched film may be used or a stretched film may be used. When using a stretched film, it is preferable to use a uniaxially or biaxially stretched substrate as long as the coating property of the coating liquid (A) and the adhesion between the substrate and the layer (A1) are not impaired. For example, the coating liquid (A) is applied and dried on the surface of the substrate uniaxially (vertically) stretched in the step (A1) to form a laminate (A1), and further uniaxially in the step (C1) described later. (Horizontal axis) Stretching and heat setting may be performed.

(Process (B1))
A process (B1) is a process of laminating | stacking the layer (B1) containing a polyvalent metal compound on the layer (A1) of the said laminated body (A1), and forming a laminated body (B1).

  As a method for forming the layer (B1) on the layer (A1) of the laminate (A1), the method described in the description of the polyvalent metal compound, preferably the method described in the description of the coating liquid (B). Can be formed.

  The thickness of the layer (B1) varies depending on the area ratio of stretching performed in the step (C1), but is usually 0.1 to 100 μm, preferably 0.1 to 70 μm, and more preferably 0. .2 to 50 μm.

In the first manufacturing method, another layer may be provided between the layer (A1) and the layer (B1).
Examples of the layer provided between the layer (A1) and the layer (B1) include a polyisocyanate layer. There is no problem when the laminate (B1) is laminated on the layer (B1) with another base material via an adhesive layer, or when it is rolled up, but a gas barrier molded laminate is produced. In the case of storing for a long time in the state of the laminate (B1) before the layer (A1) and the layer (B1) are adjacent to each other, the polycarboxylic acid polymer in the layer (A1) is Ionic crosslinking is formed by polyvalent metal ions derived from the polyvalent metal compound in the layer (B1), and the stretchability in the subsequent step (C1) tends to decrease. On the other hand, in the case where another layer such as a polyisocyanate layer is provided between the layer (A1) and the layer (B1), the formation of ionic cross-linking is delayed, and therefore the laminate (B1) in the step (C1) Stretchability can be maintained.

  In addition, the laminated body (B1) which provided the polyisocyanate layer between the layer (A1) and the layer (B1) can make a polyisocyanate layer into a thin layer by extending | stretching at a process (C1). Then, by performing the step (D), the carboxyl group of the polycarboxylic acid polymer contained in the layer (A1) reacts with the polyvalent metal ions derived from the polyvalent metal compound contained in the layer (B1). And a gas barrier molding laminate can be produced.

(Process (C1))
The step (C1) is a step of forming the step (C1) of stretching the laminate (B1) so that the area magnification is 1.1 to 100 times to form a molded laminate (C1).

  Stretching is usually performed after pre-heat treatment. Although the preheating conditions of a laminated body (B1) depend on properties, such as a glass transition point of the base material to be used and a crystallization temperature, preheating temperature is 35-250 degreeC normally, Preferably it is 40-240 degreeC. Yes, most preferably 50-230 ° C. The preheating time is usually 1 to 180 seconds, preferably 3 to 120 seconds.

  The stretching method is not particularly limited, but a method of stretching in a plane uniaxially and biaxially using a tenter, a method of molding into a container such as a cup or tray using a molding machine for deep drawing, or molding into a tire A method is mentioned. The stretching condition of the laminate depends on properties such as the glass transition point and crystallization temperature of the substrate used, but the stretching temperature is usually 35 to 250 ° C, preferably 40 to 240 ° C, most preferably. 50-230 degreeC.

Further, in the present invention, when a plastic film is used as the base material and is formed into a film or a sheet, the base material or layer (A1) is stretched by stretching by stretching after stretching. The hydrolyzed condensate of at least one compound represented by the general formula (1) contained in the layer (A1) is not only fixed in the molecular orientation produced therein but also completely hydrolyzed condensate Otherwise, the condensation reaction is promoted. Specifically, the heat setting is performed at 100 to 380 ° C. for 1 second to 60 minutes, more preferably at 100 to 350 ° C. for 5 seconds to 30 minutes, and most preferably at 100 to 300 ° C. for 30 seconds to 15 minutes. This can be done. Moreover, when a coating liquid (A) contains an inorganic salt as an additive, heat setting conditions can be eased. As a heat setting method, for example, heating can be performed in a state where the molded laminate is fixed by a hot roll heating method, a hot air superheating method, or the like.

(Process (D1))
Step (D1) is a polyvalent metal derived from the carboxyl group of the polycarboxylic acid polymer contained in the layer (A1) of the molded laminate (C1) and the polyvalent metal compound contained in the layer (B1). This is a step of reacting ions. As a process (D1), it is preferable that it is a process of performing at least 1 sort (s) of processing selected from the group which consists of a humidity control process, a boil process, and a retort process to a shaping | molding laminated body (C1).

  The retort treatment is generally a method of sterilizing microorganisms such as molds, yeasts, and bacteria for food preservation. Usually, the molded laminated body (C1) in which food is packaged is subjected to pressure sterilization treatment at 105 to 140 ° C. and 0.15 to 0.3 MPa for 5 to 120 minutes. There are two types of retort devices, a steam type using heated steam and a hot water type using pressurized superheated water, which are properly used depending on the sterilization conditions of the food product.

  On the other hand, boil treatment is a method of sterilizing with wet heat for food preservation. Usually, although it depends on the contents, the molded laminate (C1) in which food is packaged is sterilized under conditions of 60 to 100 ° C. and atmospheric pressure for 5 to 120 minutes. The boil treatment is usually performed using a hot water tank, but there are a batch type in which it is immersed in a hot water tank at a constant temperature and taken out after a predetermined time, and a continuous type in which the hot water tank is sterilized through a tunnel type.

  In addition, the humidity conditioning treatment is usually placing the molded laminate (C1) in an atmosphere of 10 to 99 ° C., atmospheric pressure, and relative humidity of 20 to 100%. The optimum range of the humidity adjustment time differs depending on the temperature and humidity. The lower the temperature and the lower the humidity, the longer the humidity adjustment is required. The higher the temperature and the humidity, the shorter the processing time. For example, humidity control is performed for 10 hours or more at 20 ° C. and 80% relative humidity, for 3 hours or more at 40 ° C. and 90% relative humidity, and for 30 minutes or more at 60 ° C. and 90% relative humidity. If it carries out, it can be set as the laminated body which usually has sufficient gas barrier property. In addition, when another substrate is laminated on the layer (B1) of the molded laminate (C1) via an adhesive, it is necessary to produce a gas barrier property that is sufficient to develop a sufficient gas barrier property compared to the case where the substrate is not laminated. The wet time becomes longer.

[Method for Producing Second Gas Barrier Molded Laminate]
The second gas barrier molded laminate production method comprises a step (A2) of applying the coating liquid (A) on the substrate and laminating the layer (A2) to form the laminate (A2). The layered product (A2) is stretched to an area magnification of 1.1 to 100 times to form a molded layered product (C2) (C2), and the layer (A2) of the molded layered product (C2) ) On which a layer (B2) containing a polyvalent metal compound is laminated to form a molded laminate (B2), and a polycarboxylic acid contained in the layer (A2) of the molded laminate (B2). And a step (D2) of reacting a carboxyl group of the acid polymer with a polyvalent metal ion derived from a polyvalent metal compound contained in the layer (B2). Hereinafter, each step will be described.

(Process (A2))
The step (A2) is a step of coating the coating liquid (A) on the substrate and laminating the layer (A2) to form the laminate (A2). The first gas barrier molding It can carry out by the method similar to the process (A1) of the manufacturing method of a laminated body.

(Process (C2))
A process (C2) is a process of extending | stretching the said laminated body (A2) so that an area magnification may be 1.1-100 times, and forming a shaping | molding laminated body (C2).

  The step (C2) can be performed under the same conditions except that in the step (C1) of the first method for producing a gas barrier molded laminate, the object to be stretched is the laminate (A2).

(Process (B2))
A process (B2) is a process of laminating | stacking the layer (B2) containing a polyvalent metal compound on the layer (A2) of the said molded laminated body (C2), and forming a molded laminated body (B2).

  As a method of forming the layer (B2) on the layer (A2) of the molded laminate (C2), the method described in the description of the polyvalent metal compound described above, preferably the description of the coating liquid (B) is described. Can be formed by a method.

As thickness of a layer (B2), it is 0.05-10 micrometers normally, Preferably it is 0.1-5 micrometers, More preferably, it is 0.1-3 micrometers.
In the second manufacturing method, another layer may be provided between the layer (A2) and the layer (B2).

(Process (D2))
Step (D2) is a polyvalent metal ion derived from the carboxyl group of the polycarboxylic acid polymer contained in the layer (A2) of the molded laminate (B2) and the polyvalent metal compound contained in the layer (B2). Is a step of reacting. The step (D2) is preferably a step in which the molded laminate (B2) is subjected to at least one treatment selected from the group consisting of humidity conditioning treatment, boil treatment, and retort treatment.

  In addition, a humidity control process, a boil process, and a retort process are the methods similar to the humidity control process, the boil process, and the retort process which were respectively described in the process (D1) of the manufacturing method of the said 1st gas barrier property molded laminated body. It can be carried out.

[Method for Producing Third Gas Barrier Molded Laminate]
The third gas barrier molded laminate production method comprises a step (A3) of forming the laminate (A3) by coating the coating liquid (A) on the substrate and laminating the layer (A3). The layered product (A3) is stretched so that the area magnification is 1.1 to 100 times to form a molded layered product (C3) (C3), and the layer (A3) of the molded layered product (C3) And a step (D3) of reacting a carboxyl group of the polycarboxylic acid-based polymer contained in (3) with a polyvalent metal ion derived from the polyvalent metal compound. Hereinafter, each step will be described.

(Process (A3))
The step (A3) is a step of coating the coating liquid (A) on the base material and laminating the layer (A3) to form the laminate (A3). The first gas barrier molding It can carry out by the method similar to the process (A1) of the manufacturing method of a laminated body.

(Process (C3))
The step (C3) is a step of stretching the laminate (A3) so that the area magnification is 1.1 to 100 times to form a molded laminate (C3), and the second gas barrier molding described above. It can carry out by the method similar to the process (C2) of the manufacturing method of a laminated body.

(Process (D3))
The step (D3) is a step of reacting the carboxyl group of the polycarboxylic acid polymer contained in the layer (A3) of the molded laminate (C3) with the polyvalent metal ion derived from the polyvalent metal compound. is there. As the step (D3), the molded laminate (C3) is immersed in a liquid containing a polyvalent metal compound and dried (hereinafter also referred to as step (D3-1)) and the molded laminate (C3). The layer (A3) is preferably at least one step selected from the group consisting of a step of spraying and drying a liquid containing a polyvalent metal compound (hereinafter also referred to as step (D3-2)).

  The step (D3-1) of immersing the molded laminate (C3) in a liquid containing a polyvalent metal compound and drying is a step (D3-1) in which the molded laminate ( By immersing and drying C3), the carboxyl group remaining in the layer (A3) stretched in step (C3) reacts with the polyvalent metal ions derived from the polyvalent metal compound to form ionic crosslinks. And forming a gas barrier molded laminate having excellent gas barrier properties.

As a process (D3-1), it is preferable to convey a shaping | molding laminated body (C3) continuously and immerse in the processing tank in which the aqueous solution containing the said polyvalent metal compound was stored.
In the step (D3-1), the treatment tank is usually an atmospheric pressure open type, and the immersion path of the molded laminate can be adjusted by adjusting the number and interval of the transport rollers.

  As the content of the polyvalent metal compound, from the viewpoint of gas barrier properties of the resulting gas barrier molded laminate, the total weight of the aqueous solution containing the polyvalent metal ions is 100 to 50% by weight, and is 0.5 to 50% by weight. It is preferably 1 to 40% by weight. When the content of the polyvalent metal compound is less than 0.5% by weight, sufficient gas barrier properties may not be obtained. When the content exceeds 50% by weight, excess polyvalent metal compound is present on the surface of the gas barrier molding laminate. It may adhere and cause poor appearance.

The liquid containing the polyvalent metal compound is preferably an aqueous solution, but may contain alcohol.
The temperature of the liquid containing the polyvalent metal ion in the step (D3-1) is not particularly limited as long as it is a temperature capable of forming ionic crosslinking, but in the case of an aqueous solution, it is preferably in the range of 5 to 100 ° C. More preferably, it is the range of 10-95 degreeC, More preferably, it is the range of 15-95 degreeC. Although immersion time changes also with the temperature of the aqueous solution containing a polyvalent metal ion, it is 0.1 second-60 minutes normally, More preferably, it is 0.1-30 minutes.

  In the step (D3-1), it is preferable to perform a washing treatment between the immersion and the drying. The method for producing a gas barrier molded laminate of the present invention can provide a molded laminate having excellent gas barrier properties even when no cleaning treatment is performed. However, the gas barrier molded laminate obtained without performing the cleaning treatment has a case where a polyvalent metal compound adheres to the surface of the laminate and the appearance is inferior, or when a substance having an odor is used as the polyvalent metal compound. The odor may be a problem.

  As the cleaning treatment, after immersing the molded laminate (C3) in an aqueous solution containing polyvalent metal ions, the excess polyvalent metal compound adhering to the surface of the molded laminate (C3) after the immersion, etc. If it can remove, there will be no limitation in particular, You may let the washing tank which stores a washing | cleaning liquid pass, and you may spray a washing | cleaning liquid in shower shape.

The cleaning liquid used for the cleaning treatment is not particularly limited as long as it can remove excess polyvalent metal compound and the like attached during immersion, and tap water, distilled water, ion-exchanged water, or the like can be used. Moreover, the temperature of a washing | cleaning liquid is 5-100 degreeC normally, and washing | cleaning time is 0.1 to 60 minutes.

  The method of drying the molded laminate (C3) after immersion after the immersion or washing treatment is not particularly limited, but is a method of natural drying, a method of drying in an oven set at a predetermined temperature, an arch dryer, Examples thereof include a method using a dryer such as a floating dryer, a drum dryer, and an infrared dryer. The drying conditions can be appropriately selected depending on the drying method and apparatus, but are usually in the range of 40 to 250 ° C. and 0.5 seconds to 10 minutes.

  The step (D3-2) of spraying and drying a liquid containing a polyvalent metal compound on the layer (A3) of the molded laminated body (C3) is a step of spraying a liquid containing a polyvalent metal compound, preferably an aqueous solution, into the molded laminated body ( By spraying on the layer (A3) of C3) and drying, the carboxyl groups remaining in the layer (A3) stretched in the step (C3) and the polyvalent metal ions derived from the polyvalent metal compound are ionized. It is a step of forming a gas barrier property molded laminate having excellent gas barrier properties by forming a crosslink.

  As the step (D3-2), a high-humidity treatment tank for spraying a liquid containing a polyvalent metal compound, preferably an aqueous solution, is provided, and the molded laminate (C3) is continuously conveyed to the high-humidity treatment tank in-line. It is preferable to spray a liquid containing a polyvalent metal compound, preferably an aqueous solution.

  When a high-humidity treatment tank for spraying a liquid containing a polyvalent metal compound, preferably an aqueous solution, is used, it is contained in a liquid containing a carboxyl group of the polycarboxylic acid polymer and the polyvalent metal compound, preferably an aqueous solution. Ion crosslinking formed from the polyvalent metal ions of the polyvalent metal compound can be efficiently formed in a short time. The humidification by spraying is preferably carried out by spraying a liquid containing a fine polyvalent metal compound in a shower form, preferably an aqueous solution, and making it into a humid state by the mist.

  The humid processing tank is basically provided with one or many spraying ports (spraying nozzles) at the upper part of the processing tank, and a liquid containing a polyvalent metal compound, preferably an aqueous solution, is sprayed from the spraying port in a shower shape. The inside of the treatment tank is brought into a humid state by a liquid containing the atomized polyvalent metal compound, preferably an aqueous solution.

  Alternatively, a liquid containing a polyvalent metal compound, preferably an aqueous solution, is sprayed with heated steam, and a liquid containing the polyvalent metal compound, preferably an aqueous solution, is sprayed in a high-temperature and high-humidity treatment tank having a relative humidity of 80% or more. The method of doing is mentioned. By using these methods, the above-described ionic crosslinking can be efficiently formed in a short time.

  The liquid containing the polyvalent metal compound used in the step (D3-2), preferably the content of the polyvalent metal compound in the aqueous solution is 100% of the total weight of the liquid containing the polyvalent metal compound, preferably 100% from the viewpoint of gas barrier properties. In terms of weight percent, it is 0.1 to 50 weight percent, preferably 1 to 30 weight percent, and most preferably 3 to 20 weight percent. If the content of the polyvalent metal compound is less than 0.1% by weight, sufficient gas barrier properties may not be obtained. If the content is greater than 50% by weight, excess polyvalent metal compound adheres to the surface of the gas barrier molding laminate. However, the appearance tends to be poor and a long-time cleaning process tends to be required.

  In the step (D3-2), the temperature of the aqueous solution containing the polyvalent metal compound at the time of spraying is usually 100 ° C. or less which does not exceed the boiling point of water. If the boiling point is exceeded, processing under high pressure is required, and a special processing device is required. The temperature range is preferably 5 to 100 ° C, more preferably 10 to 95 ° C, and particularly preferably 15 to 95 ° C.

  Below the above range, it may take too much time to form ionic crosslinks, which is not suitable for industrial production. On the other hand, if the above range is exceeded, processing under high pressure is required, and a special processing device is required.

  In the step (D3-2), the spraying time varies depending on the temperature of the aqueous solution containing the polyvalent metal compound to be sprayed, etc., but when the aqueous solution containing the polyvalent metal compound is sprayed at room temperature, it is usually 0.1. Second to 60 minutes, preferably 0.1 second to 10 minutes, and more preferably 0.1 second to 1 minute.

  In the step (D3-2), it is preferable to perform a washing treatment between spraying and drying. The method for producing a gas barrier molded laminate of the present invention can provide a laminate excellent in gas barrier properties even when no cleaning treatment is performed. However, the gas barrier molded laminate obtained without performing the cleaning treatment has a case where a polyvalent metal compound adheres to the surface of the laminate and the appearance is inferior, or when a substance having an odor is used as the polyvalent metal compound. The odor may be a problem.

As the cleaning treatment, the cleaning method described in the step (D3-1) can be used.
The method for drying the sprayed molded laminate (C3) after spraying or washing treatment is not particularly limited, and the drying method described in the step (D3-1) can be used.

[Method for Producing Fourth Gas Barrier Molded Laminate]
In the fourth method for producing a gas barrier molded laminate, a layer (B4) containing a polyvalent metal compound is laminated on a base material to form a laminate (B4) (B4), and the laminate ( A step (A4) of applying the coating liquid (A) on the layer (B4) of B4) to laminate the layer (A4) to form a laminate (A4), and the laminate (A4). The step (C4) of forming the molded laminate (C4) by stretching so that the area magnification is 1.1 to 100 times, and the polycarboxylic acid type contained in the layer (A4) of the molded laminate (C4) And a step (D4) of reacting a carboxyl group of the polymer with a polyvalent metal ion derived from the polyvalent metal compound contained in the layer (B4). Hereinafter, each step will be described.

(Process (B4))
A process (B4) is a process of laminating | stacking the layer (B4) containing a polyvalent metal compound on a base material, and forming a laminated body (B4).

  As a method of forming the layer (B4) on the substrate, it can be formed by the method described in the description of the polyvalent metal compound, preferably the method described in the description of the coating liquid (B).

(Process (A4))
The step (A4) is to apply the coating liquid (A) on the layer (B4) of the laminate (B4) to laminate the layer (A4) to form a laminate (A4). .

  As the step (A4), the same conditions except that in the step (A1) of the manufacturing method of the first gas barrier molded laminate, the object to be coated with the coating liquid (A) is on the layer (B4). Can be done.

In the fourth manufacturing method, another layer may be provided between the layer (B4) and the layer (A4). As another layer, the polyisocyanate layer similar to the 1st manufacturing method is illustrated.
(Process (C4))
A process (C4) is a process of extending | stretching the said laminated body (A4) so that an area magnification may be 1.1-100 times, and forming a shaping | molding laminated body (C4).

  The step (C4) can be performed under the same conditions except that in the step (C1) of the first method for producing a gas barrier molded laminate, the object to be stretched is the laminate (A4).

(Process (D4))
Step (D4) is a polyvalent metal derived from the carboxyl group of the polycarboxylic acid polymer contained in the layer (A4) of the molded laminate (C4) and the polyvalent metal compound contained in the layer (B4). This is a step of reacting ions. As a process (D4), it is preferable that it is a process which performs at least 1 sort (s) of processing selected from the group which consists of a humidity control process, a boil process, and a retort process to a molded laminated body (C4).

  In addition, a humidity control process, a boil process, and a retort process are the methods similar to the humidity control process, the boil process, and the retort process which were respectively described in the process (D1) of the manufacturing method of the said 1st gas barrier property molded laminated body. It can be carried out.

  Excellent gas barrier properties can be imparted to the gas barrier molding laminate obtained by performing the steps (D1) to (D4) in the first to fourth gas barrier molding laminates.

  Since the first to fourth methods for producing gas barrier molded laminates use the coating liquid (A) containing a plasticizer, they are excellent in moldability, and various shapes of gas barrier molded laminates can be produced. Among the manufacturing methods of the first to fourth gas barrier molded laminates, the first, second, and fourth gas barrier molded laminates are preferable from the viewpoint of the gas barrier properties of the obtained gas barrier molded laminate.

  In addition, before performing a process (C1) and a process (C4) in the manufacturing method of the 1st and 4th gas-barrier shaping | molding laminated body, on the layer (B1) of a laminated body (B1), and the layer of a laminated body (A4) Another substrate can be laminated on the (A4) via an adhesive. In particular, when forming into a bottle, a cup, a tray, a container, or a tank, it is preferable to stretch in the step (C1) and the step (C4) after laminating from the viewpoint of gas barrier properties and appearance. Examples of the laminating method include known laminating methods, and specifically include a dry laminating method, a wet laminating method, and an extrusion laminating method.

  The aspect of the laminate is not particularly limited and can be appropriately selected depending on the application. Specific embodiments of the first production method include, for example, substrate / layer (A) / layer (B) / polyolefin, substrate / layer (A) / layer (B) / nylon, substrate / layer (A ) / Layer (B) / nylon / polyolefin, substrate / layer (A) / layer (B) / metal-deposited nylon / polyolefin, and the like. As a specific aspect in the fourth manufacturing method, there is a laminated configuration in which the order of the layer (A) and the layer (B) in the specific aspect in the first manufacturing method is switched.

  Moreover, in the manufacturing method of the 1st-4th gas-barrier shaping | molding laminated body, another base material can also be laminated before and after process (D1), (D2), (D4), or after process (D3). . By laminating with another base material, performances such as strength, sealing property, easy-opening property at the time of sealing, design property, light blocking property, moisture resistance and the like can be imparted. Examples of the laminating method include the above-described methods. The aspect of the laminate is not particularly limited and can be appropriately selected depending on the application. Specific embodiments of the first and second production methods include, for example, substrate / layer (A) / layer (B) / polyolefin, substrate / layer (A) / layer (B) / nylon, substrate / layer. (A) / layer (B) / nylon / polyolefin, substrate / layer (A) / layer (B) / metal-deposited nylon / polyolefin, and the like. Moreover, as a specific aspect in the third manufacturing method, an aspect in which the layer (B) is removed from the above-described laminated structure is exemplified. Furthermore, as a specific aspect in the fourth manufacturing method, there may be mentioned an aspect in which the layer (A) and the layer (B) of the specific aspect in the first and second manufacturing methods are laminated in the reverse order.

  Moreover, in the manufacturing method of the said 1st-4th gas-barrier shaping | molding laminated body, before performing a process (D1)-(D4), a laminated body may be shape | molded previously in a bag shape and a packaged article may be packaged. . In particular, when the package is food, etc., the food is packaged and then subjected to retort treatment or boil treatment as steps (D1), (D2), and (D4) to sterilize the food at the same time. Can do.

<Gas barrier molded laminate>
The gas barrier molded laminate of the present invention can be obtained by the above-described first to fourth gas barrier molded laminate manufacturing methods.

  The gas barrier molded laminate of the present invention is excellent in gas barrier properties and easily deteriorates due to the influence of oxygen, etc., high temperature sterilization of packaging materials such as precision metal parts such as foods, beverages, medicines, pharmaceuticals and electronic parts, boil, retort, etc. It can be suitably used as a packaging material for articles requiring treatment, or as a packaging body thereof.

The gas barrier molded laminate of the present invention generally has an oxygen permeability at a temperature of 20 ° C. and a relative humidity of 80% of 300 cm ³ (STP) / m ² · day · MPa or less, preferably 100 cm ³ (STP). / M ² · day · MPa or less, more preferably 10 cm ³
(STP) / m ² · day · MPa or less. The oxygen permeability of the gas barrier molded laminate of the present invention is preferably as low as possible, and the lower limit thereof is not particularly limited. However, the gas barrier molded laminate of the present invention has a temperature of 20 ° C. and a relative humidity of 80%. The measured oxygen permeability is usually 0.01 cm ³ (STP) / m ² · day · MPa or more.
[Example]
The present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

In addition, the measurement and evaluation about the gas-barrier molded laminated body (Z) obtained by the Example and the comparative example were performed as follows.
(1) Gas barrier property About the obtained gas barrier property laminated body (Z), oxygen permeability measuring apparatus (Modern
The oxygen transmission rate was measured under the conditions of a temperature of 20 ° C. and a relative humidity of 80% using OXTRAN 2/20 manufactured by Control. The measurement method was based on JIS K-7126, B method (isobaric method), and ASTM D3985-81, and the measured value was expressed in units [cm ³ (STP) / m ² · day · MPa]. Note that (STP) means standard conditions (0 ° C., 1 atm) for defining the volume of oxygen.

<Manufacture of coating liquid (A-1)>
A polyacrylic acid aqueous solution (PAA: manufactured by Toagosei Co., Ltd., Aron A-10H, solid content concentration: 25 wt%) having a number average molecular weight of 200,000 is dissolved in 120 g of distilled water, and the solid content concentration in the aqueous solution is 10 wt% A polyacrylic acid aqueous solution was obtained.

Next, 6.84 g of tetramethoxysilane (TMOS) is dissolved in 8.2 g of methanol,
Subsequently, after dissolving 1.36 g of γ-glycidoxypropyltrimethoxysilane (GPTMS), 0.51 g of distilled water and 1.27 g of 0.1N hydrochloric acid were added to prepare a sol, and this was stirred. A hydrolysis and condensation reaction was performed at 10 ° C. for 1 hour to obtain a hydrolysis-condensation product.

  The obtained hydrolyzed condensate was diluted with 18.5 g of distilled water and then added to 63.4 g of the 10 wt% aqueous polyacrylic acid solution with stirring, and 1.3 g of glycerin (manufactured by Wako Pure Chemical Industries) as a plasticizer. Was added to obtain a coating liquid (A-1).

<Production of Gas Barrier Molded Laminate (Z-1)>
Polyethylene terephthalate (hereinafter also referred to as PET) (manufactured by Vordian Eastman, 9921) is melt-extruded by a T-die method at a temperature of 270 ° C., cooled by a cooling roll at 15 ° C., and an unstretched PET film having a thickness of 120 μm. Was deposited. This unstretched PET film was stretched three times in the longitudinal direction between a pair of 87 ° C. rolls having different peripheral speeds.

  Next, after coating the coating liquid (A-1) on the obtained film surface using a gravure coater, the coated surface is dried at 100 ° C. for 15 seconds to form a layer (A-1), and a laminated film (Laminate) (A2-1) was obtained. The obtained laminated film (A2-1) was preheated at 100 ° C. for 30 seconds, and then stretched 3 times in the transverse direction at a stretching temperature of 100 ° C. Thereafter, heat setting was carried out at 200 ° C. for 5 minutes to obtain a molded laminate (C2-1) having a PET film thickness of 13 μm and a layer (A2-1) thickness of 0.5 μm.

  Fine zinc oxide dispersion (coating liquid (B-1)) (manufactured by Sumitomo Osaka Cement, ZS303, average particle diameter 0.02 μm) on the surface of the layer (A2-1) of the obtained molded laminate (C2-1) , A solid content concentration of 30% by weight, and a dispersion solvent toluene) were coated using a gravure coater so that the thickness after drying was 0.5 μm, and then dried at 90 ° C. for 2 minutes to form a coating solution (B-1 ) -Derived layer (B2-1) and having a configuration of [PET (13 μm) / layer (A2-1) (0.5 μm) / layer (B2-1) (0.5) μm] A laminate (B2-1) was obtained.

  On the surface of the layer (B2-1) of the obtained molded laminate (B2-1), an unstretched polypropylene film (hereinafter, also referred to as CPP) (manufactured by Toray Film Processing Co., Ltd., Treffan NO ZK93FM, thickness 60 μm). Molding having a configuration of [molded laminate (B2-1) / adhesive layer / CPP (60 μm)] using a two-component adhesive (made by Mitsui Takeda Polyurethane, A620 and A65) by a dry lamination method. A laminate (B2-1 ′) was obtained.

Two pieces of the molded laminate (B2-1 ′) were cut out in a size of 15 cm × 20 cm, and the CPPs were overlapped to form a bag by heat-sealing three sides, thereby producing a flat pouch.
After injecting 250 ml of water, the remaining one side was heat-sealed to produce a water-filled pouch. This pouch was retorted at 120 ° C. for 40 minutes using a hot water retort kettle. Thereafter, the water-filled pouch was taken out, the heat seal portion was cut out, the injected water was extracted, the water adhering to the film was wiped off, and a gas barrier molded laminate (Z-1) was obtained.

The gas barrier property was evaluated for the gas barrier molded laminate (Z-1).
Tables 1 and 2 show the configuration of the gas barrier molded laminate (Z-1), and Table 3 shows the evaluation results.

<Manufacture of coating liquid (A-2)>
In the production of the coating liquid (A-1) of Example 1, 1.3 g of glycerin is 1.5 g of polyvinyl alcohol (manufactured by Wako Pure Chemical Industries, average polymerization degree 1,500, hereinafter also referred to as PVA).
A coating solution (A-2) was obtained in the same manner except that the coating solution was changed to.

<Production of Gas Barrier Molded Laminate (Z-2)>
In the production of the gas barrier molded laminate (Z-1) of Example 1, the same applies except that the layer (A-2) was formed by replacing the coating liquid (A-1) with the coating liquid (A-2). To obtain a molded laminate (B2-2) having a structure of [PET (13 μm) / layer (A2-2) (0.5 μm) / layer (B2-2) (0.5) μm], [ Molded laminate (B2-2 ′) having a configuration of molded laminate (B2-2) / adhesive layer / CPP (60 μm)] was obtained.

The molded laminate (B2-2 ′) was retorted in the same manner as in Example 1 to obtain a gas barrier molded laminate (Z-2).
The gas barrier property was evaluated for the gas barrier property molded laminate (Z-2).

  Tables 1 and 2 show the configuration of the gas barrier molded laminate (Z-2), and Table 3 shows the evaluation results.

<Manufacture of coating liquid (A-3)>
20 g of polyacrylic acid aqueous solution with a number average molecular weight of 200,000 (PAA: manufactured by Toagosei Co., Ltd., Aron A-10H, solid concentration 25 wt%) was dissolved in 58.9 g of distilled water, and then aminopropyltrimethoxysilane (APTMS: Aldrich). (Product) 0.44 g was added, and 1.3 g of glycerin was further added, followed by stirring to obtain a coating liquid (A-3).

<Production of Gas Barrier Molded Laminate (Z-3)>
In the same manner as in Example 1, an unstretched PET film having a thickness of 120 μm was formed, and then stretched three times in the longitudinal direction between a pair of 87 ° C. rolls having different peripheral speeds.

  Next, the fine particle zinc oxide dispersion liquid (coating liquid B-1) used in Example 1 was coated on the obtained film surface using a gravure coater, and then the coated surface was dried at 90 ° C. for 2 minutes. A layer (B4-1) derived from the coating liquid (B-1) was formed to obtain a laminate (B4-1). Next, the coating liquid (A-3) was applied onto the layer (B4-1) of the laminate (B4-1) using a gravure coater, and then the coated surface was dried at 100 ° C. for 15 seconds to form a layer (A4-1) ) To obtain a laminate (A4-1).

The obtained laminate (A4-1) was preheated at 100 ° C. for 30 seconds, and then stretched 3 times in the transverse direction at a stretching temperature of 100 ° C.
Thereafter, heat-fixing was performed at 200 ° C. for 5 minutes, and a molded laminate (C4-) having a configuration of [PET (13 μm) / layer (B4-1) (0.5 μm) / layer (A4-1) (0.5 μm)]. 1) was obtained.

  On the surface of the layer (A4-1) of the obtained molded laminate (C4-1), lamination was applied in the same manner as in Example 1, and [molded laminate (C4-1) / adhesive layer / CPP (60 μm )] To obtain a molded laminate (C4-1 ′).

The molded laminate (C4-1 ′) was retorted in the same manner as in Example 1 to obtain a gas barrier molded laminate (Z-3).
The gas barrier property was evaluated for the gas barrier molded laminate (Z-3).

  Tables 1 and 2 show the configuration of the gas barrier molded laminate (Z-3), and Table 3 shows the evaluation results.

<Manufacture of coating liquid (A-4)>
In the production of the coating liquid (A-2) of Example 2, 1.5 g of PVA was replaced with 2.1 g of reduced starch saccharified product (PO20 manufactured by Towa Kasei Kogyo Co., Ltd., solid content concentration 70 wt%, hereinafter also referred to as starch). In the same manner, a coating liquid (A-4) was obtained.

<Production of Gas Barrier Molded Laminate (Z-4)>
PET was melt-extruded by a T-die method at a temperature of 270 ° C., cooled by a cooling roll at 15 ° C., and an unstretched PET film having a thickness of 120 μm was formed. The unstretched PET film was stretched three times in the longitudinal direction between a pair of 87 ° C. rolls having different peripheral speeds.

  Then, after coating the coating liquid (A-4) on the obtained film surface using a gravure coater, the coated surface is dried at 100 ° C. for 15 seconds to form a layer (A1-1) A body (A1-1) was obtained.

  A gravure coater is formed on the surface of the layer (A1-1) of the obtained laminate (A1-1) so that the thickness after drying the fine zinc oxide dispersion (coating solution (B-1)) becomes 1 μm. After using, it was made to dry at 90 degreeC for 2 minute (s), the layer (B1-1) derived from a coating liquid (B-1) was formed, and the laminated body (B1-1) was obtained.

The obtained laminate (B1-1) was preheated at 100 ° C. for 30 seconds, and then stretched 3 times in the transverse direction at a stretching temperature of 100 ° C.
Thereafter, heat-fixing was performed at 200 ° C. for 5 minutes, and a molded laminate having a configuration of [PET (13 μm) / layer (A1-1) (0.5 μm) / layer (B1-1) (0.3 μm)] (C1- 1) was obtained.

  On the surface of the layer (B1-1) of the obtained molded laminate (C1-1), lamination was applied in the same manner as in Example 1, and [molded laminate (C1-1) / adhesive layer / CPP (60 μm )] To obtain a molded laminate (C1-1 ′).

The molded laminate (C1-1 ′) was retorted in the same manner as in Example 1 to obtain a gas barrier molded laminate (Z-4).
The gas barrier property was evaluated for the gas barrier molded laminate (Z-4).

  Tables 1 and 2 show the configuration of the gas barrier molded laminate (Z-4), and Table 3 shows the evaluation results.

<Production of Gas Barrier Molded Laminate (Z-5)>
PET was melt-extruded by a T-die method at a temperature of 270 ° C., cooled by a cooling roll at 15 ° C., and an unstretched PET film having a thickness of 120 μm was formed.

  Subsequently, after coating the coating liquid (A-1) on the obtained film surface using a gravure coater, the coated surface is dried at 100 ° C. for 15 seconds to form a layer (A1-2) A body (A1-2) was obtained.

  A gravure coater is applied on the surface of the layer (A1-2) of the obtained laminate (A1-2) so that the thickness after drying the fine particle zinc oxide dispersion (coating solution (B-1)) becomes 1 μm. After coating using, it was made to dry at 90 degreeC for 2 minute (s), the layer (B1-2) derived from a coating liquid (B-2) was formed, and the laminated body (B1-2) was obtained.

The obtained laminate (B1-2) was heat-softened to 110 ° C. using a deep drawing type high-speed automatic vacuum packaging machine (FV-603 type, manufactured by Omori Machine Industry Co., Ltd.), and then vacuum-molded to obtain a molded product. A container-shaped molded laminate (C1-2) having a size of φ100 mm and a depth of 10 mm was obtained. The area magnification of the container was 1.4 times.

The obtained molded laminate (C1-2) was held in a constant temperature bath at 40 ° C. and 90% relative humidity for 2 days to obtain a gas barrier molded laminate (Z-5).
The gas barrier property was evaluated for the gas barrier molded laminate (Z-5).

  Tables 1 and 2 show the configuration of the gas barrier molded laminate (Z-5), and Table 3 shows the evaluation results.

<Manufacture of coating liquid (A-5)>
In manufacturing the coating liquid (A-3) of Example 3, it carried out similarly except having replaced glycerol 1.3g with PVA1.5g, and obtained coating liquid (A-5).

<Production of Gas Barrier Molded Laminate (Z-6)>
After coating the coating liquid (A-5) using a gravure coater on an unstretched polypropylene sheet (CPP, TORAYFAN NO ZK93FM, manufactured by Toray Film Co., Ltd., 60 μm thick), the coated surface is dried at 100 ° C. for 15 seconds. And forming a layer (A1-3) to obtain a laminate (A1-3).

  A gravure coater is formed on the surface of the layer (A1-3) of the obtained laminate (A1-3) so that the thickness after drying the fine particle zinc oxide dispersion (coating solution (B-1)) becomes 1 μm. After coating using, it was made to dry at 90 degreeC for 2 minute (s), the layer (B1-3) originating in a coating liquid (B-2) was formed, and the laminated body (B1-3) was obtained.

  On the surface of the layer (B1-3) of the obtained laminate (B1-3), a laminate was applied in the same manner as in Example 1, and [laminate (B1-3) / adhesive layer / CPP (60 μm)]. A laminate (B1-3 ′) having the following structure was obtained.

  The obtained laminate (B1-3 ′) was heated and softened to 210 ° C. using a vacuum / pressure forming machine (PF-2940 model manufactured by Tokatsu Yamato Seisakusho), melted and drawn, and the size of the molded product was reduced. A container-shaped molded laminate (C1-3) having a width of 180 mm, a length of 120 mm, and a depth of 50 mm was obtained. The area magnification of the container was 2.4 times.

The resulting molded laminate (C1-3) was retorted in the same manner as in Example 1 to obtain a gas barrier molded laminate (Z-6).
The gas barrier property was evaluated for the gas barrier molded laminate (Z-6).

  Tables 1 and 2 show the configuration of the gas barrier molded laminate (Z-6), and Table 3 shows the evaluation results.

<Production of Gas Barrier Molded Laminate (Z-7)>
PET was melt-extruded by a T-die method at a temperature of 270 ° C., cooled by a cooling roll at 15 ° C., and an unstretched PET film having a thickness of 120 μm was formed. The unstretched PET film was stretched three times in the longitudinal direction between a pair of 87 ° C. rolls having different peripheral speeds.

  Subsequently, after coating the coating liquid (A-5) used in Example 6 on the obtained film surface using a gravure coater, the coated surface was dried at 100 ° C. for 15 seconds, and the layer (A3- 1) was formed to obtain a laminate (A3-1).

The obtained laminate (A3-1) was preheated at 100 ° C. for 30 seconds, and then stretched three times in the transverse direction at a stretching temperature of 100 ° C.
Thereafter, heat setting was performed at 200 ° C. for 5 minutes to obtain a molded laminate (C3-1) having a PET film thickness of 13 μm and a layer (A3-1) thickness of 0.5 μm.

  The obtained molded laminate (C3-1) was immersed in a 10 wt% zinc acetate-containing aqueous solution heated to 60 ° C. for 10 seconds, then washed with tap water, and then dried at 90 ° C. for 2 minutes [PET A gas barrier molded laminate (Y-7) having a structure of (13 μm) / layer (A3-1) (after zinc acetate immersion)] was obtained.

  On the surface of the layer (A3-1) (after zinc acetate immersion) of the obtained gas barrier molding laminate (Y-7), lamination was applied in the same manner as in Example 1, and [Gas barrier molding laminate (Y- 7) / Adhesive layer / CPP (60 μm)] to obtain a gas barrier molded laminate (Z-7).

The gas barrier property was evaluated for the gas barrier molded laminate (Z-7).
Tables 1 and 2 show the configuration of the gas barrier molded laminate (Z-7), and Table 3 shows the evaluation results.
[Comparative Example 1]
<Manufacture of coating liquid (A-6)>
In manufacturing the coating liquid (A-1) of Example 1, it carried out similarly except not having added glycerin, and obtained coating liquid (A-6).

<Production of Gas Barrier Molded Laminate (Z-8)>
In the production of the gas barrier molded laminate (Z-7) of Example 7, the same procedure was followed except that the layer (A3-1C) was formed by replacing the coating liquid (A-5) with the coating liquid (A-6). To obtain a molded laminate (C3-1C) having a PET film thickness of 13 μm and a layer (A3-1C) thickness of 0.5 μm, [PET (13 μm) / layer (A3-1C) (zinc acetate immersion) Gas barrier molding laminate (Y-8) having the configuration of [after]] and gas barrier molding laminate (Z) (Z-8 (60 μm)) / [adhesive layer / CPP (60 μm)]. -8) was obtained.

The gas barrier property was evaluated for the gas barrier molded laminate (Z-8).
Tables 1 and 2 show the configuration of the gas barrier molded laminate (Z-8), and Table 3 shows the evaluation results.
Although the comparative example 1 is inferior in gas barrier property compared with an Example, since it is not using the plasticizer, this is considered because the layer (A3-1C) cracked when extended | stretched.

[Comparative Example 2]
<Manufacture of coating liquid (A-7)>
In the manufacture of the coating liquid (A-3) of Example 3, it carried out similarly except not having added glycerol, and obtained coating liquid (A-7).

<Production of Gas Barrier Molded Laminate (Z-9)>
In the production of the gas barrier molded laminate (Z-7) of Example 7, the layer (A3-2C) is formed by changing the coating liquid (A-5) to the coating liquid (A-7), and further 10 wt. A molded laminate (C3-2C) having a PET film thickness of 13 μm and a layer (A3-2C) thickness of 0.5 μm was obtained in the same manner except that a calcium acetate aqueous solution was used instead of water containing% zinc acetate. And [Gas barrier molding laminate (Y-9) and [Gas barrier molding laminate (Y-9) / adhesive] having a configuration of [PET (13 μm) / layer (A3-2C) (after calcium acetate immersion)]. Gas-barrier molded laminate (Z-9) having the structure of layer / CPP (60 μm)] was obtained.

The gas barrier property was evaluated for the gas barrier molded laminate (Z-9).
Tables 1 and 2 show the configuration of the gas barrier molded laminate (Z-9), and Table 3 shows the evaluation results.
Although the comparative example 2 is inferior in gas barrier property compared with an Example, since it is not using the plasticizer, this is considered because the layer (A3-2C) cracked when extended | stretched.

[Comparative Example 3]
<Production of Gas Barrier Molded Laminate (Z-10)>
Using the coating liquid (A-6) used in Comparative Example 1, coating the coating liquid (A-6) on PET in the same manner as in the production of the gas barrier molded laminate (Z-1) in Example 1. After forming a layer (A2-1C) to obtain a laminate (A2-1C), stretching and heat setting are performed, the PET film thickness is 13 μm, and the layer (A2-1C) thickness is 0.5 μm. A molded laminate (C2-1C) was obtained. A layer (B2-1C) is formed on the layer (A2-1C) of the obtained molded laminate (C2-1C) using a fine particle zinc oxide dispersion (coating solution (B-1)), and [PET A molded laminate (B2-1C) having a configuration of (13 μm) / layer (A2-1C) (0.5 μm) / layer (B2-1C)] was obtained.

  Further, the laminate (B2-1C) of the obtained molded laminate (B2-1C) was laminated in the same manner as in Example 1, and [molded laminate (B2-1C) / adhesive layer / CPP (60 μm )] To obtain a molded laminate (B2-1C ′).

The obtained molded laminate (B2-1C ′) was retorted in the same manner as in Example 1 to obtain a gas barrier molded laminate (Z-10).
The gas barrier property of the gas barrier molded laminate (Z-10) was evaluated.

Tables 1 and 2 show the configuration of the gas barrier molded laminate (Z-10), and Table 3 shows the evaluation results.
Although the comparative example 3 is inferior in gas barrier property compared with an Example, since it is not using the plasticizer, this is considered because the layer (A2-1C) cracked when extended | stretched.

Claims (16)

A coating liquid (A) containing a polycarboxylic acid polymer, a hydrolysis condensate of at least one compound represented by the following general formula (1), and a plasticizer is applied on a substrate. A step (A1) of laminating the layer (A1) to form a laminate (A1);
A step (B1) of laminating a layer (B1) containing a polyvalent metal compound on the layer (A1) of the laminate (A1) to form a laminate (B1);
Stretching the laminate (B1) so that the area magnification is 1.1 to 100 times to form a molded laminate (C1) (C1);
A step of reacting a carboxyl group of the polycarboxylic acid polymer contained in the layer (A1) of the molded laminate (C1) with a polyvalent metal ion derived from the polyvalent metal compound contained in the layer (B1) ( D1) and a method for producing a gas barrier molded laminate.
M ¹ (OR ¹ ) _n R ² _mnts X ¹ _t Z ¹ _s (1)
(In the general formula (1), M ¹ is Si, Al, Ti or Zr, R ¹ is an alkyl group having 1 to 6 carbon atoms, R ² is an alkyl group having 1 to 10 carbon atoms, an aralkyl group, An aryl group,
An alkenyl group, an alkyl group substituted with an acryloxy group, or an alkyl group substituted with a methacryloxy group, X ¹ is a halogen atom, Z ¹ is a glycidyloxy group, an epoxy group, a mercapto group, a hydroxyl group, an amino group, Or it is an organic group containing an isocyanate group. M represents the valence of M ¹ , n represents an integer of 0 to m, s is 0 or 1,
t represents an integer of 0 to m. Further, n + t ≠ 0, and 1 ≦ n + t + s ≦ m.
When a plurality of R ¹ , R ² and X ¹ are present, each R ¹ , R ² and X ¹ may be the same or different. ) On the base material, a coating liquid (A) containing a polycarboxylic acid polymer, a hydrolysis condensate of at least one compound represented by the following general formula (1), and a plasticizer is applied. A step (A2) of laminating the layer (A2) to form a laminate (A2);
Stretching the laminate (A2) to an area magnification of 1.1 to 100 times to form a molded laminate (C2) (C2);
A step (B2) of laminating a layer (B2) containing a polyvalent metal compound on the layer (A2) of the molded laminate (C2) to form a molded laminate (B2);
A step of reacting a carboxyl group of the polycarboxylic acid polymer contained in the layer (A2) of the molded laminate (B2) with a polyvalent metal ion derived from the polyvalent metal compound contained in the layer (B2) ( D2) and a method for producing a gas barrier molded laminate.
M ¹ (OR ¹ ) _n R ² _mnts X ¹ _t Z ¹ _s (1)
(In the general formula (1), M ¹ is Si, Al, Ti or Zr, R ¹ is an alkyl group having 1 to 6 carbon atoms, R ² is an alkyl group having 1 to 10 carbon atoms, an aralkyl group, An aryl group,
An alkenyl group, an alkyl group substituted with an acryloxy group, or an alkyl group substituted with a methacryloxy group, X ¹ is a halogen atom, Z ¹ is a glycidyloxy group, an epoxy group, a mercapto group, a hydroxyl group, an amino group, Or it is an organic group containing an isocyanate group. M represents the valence of M ¹ , n represents an integer of 0 to m, s is 0 or 1,
t represents an integer of 0 to m. Further, n + t ≠ 0, and 1 ≦ n + t + s ≦ m.
When a plurality of R ¹ , R ² and X ¹ are present, each R ¹ , R ² and X ¹ may be the same or different. ) On the base material, a coating liquid (A) containing a polycarboxylic acid polymer, a hydrolysis condensate of at least one compound represented by the following general formula (1), and a plasticizer is applied. A step (A3) of laminating the layer (A3) to form a laminate (A3);
The laminate (A3) is stretched so that the area magnification is 1.1 to 100 times, and a molded laminate (
A step (C3) of forming C3);
A step (D3) of reacting a carboxyl group of the polycarboxylic acid polymer contained in the layer (A3) of the molded laminate (C3) with a polyvalent metal ion derived from the polyvalent metal compound. A method for producing a gas-barrier molded laminate, which is characterized.
M ¹ (OR ¹ ) _n R ² _mnts X ¹ _t Z ¹ _s (1)
(In the general formula (1), M ¹ is Si, Al, Ti or Zr, R ¹ is an alkyl group having 1 to 6 carbon atoms, R ² is an alkyl group having 1 to 10 carbon atoms, an aralkyl group, An aryl group,
An alkenyl group, an alkyl group substituted with an acryloxy group, or an alkyl group substituted with a methacryloxy group, X ¹ is a halogen atom, Z ¹ is a glycidyloxy group, an epoxy group, a mercapto group, a hydroxyl group, an amino group, Or it is an organic group containing an isocyanate group. M represents the valence of M ¹ , n represents an integer of 0 to m, s is 0 or 1,
t represents an integer of 0 to m. Further, n + t ≠ 0, and 1 ≦ n + t + s ≦ m.
When a plurality of R ¹ , R ² and X ¹ are present, each R ¹ , R ² and X ¹ may be the same or different. ) A step (B4) of laminating a layer (B4) containing a polyvalent metal compound on a substrate to form a laminate (B4);
A coating comprising a polycarboxylic acid polymer, a hydrolysis condensate of at least one compound represented by the following general formula (1), and a plasticizer on the layer (B4) of the laminate (B4). A step (A4) of applying the liquid (A) to laminate the layer (A4) to form a laminate (A4);
Stretching the laminate (A4) to an area magnification of 1.1 to 100 times to form a molded laminate (C4) (C4);
A step of reacting a carboxyl group of the polycarboxylic acid polymer contained in the layer (A4) of the molded laminate (C4) with a polyvalent metal ion derived from the polyvalent metal compound contained in the layer (B4) ( D4) and a method for producing a gas barrier molded laminate.
M ¹ (OR ¹ ) _n R ² _mnts X ¹ _t Z ¹ _s (1)
(In the general formula (1), M ¹ is Si, Al, Ti or Zr, R ¹ is an alkyl group having 1 to 6 carbon atoms, R ² is an alkyl group having 1 to 10 carbon atoms, an aralkyl group, An aryl group,
An alkenyl group, an alkyl group substituted with an acryloxy group, or an alkyl group substituted with a methacryloxy group, X ¹ is a halogen atom, Z ¹ is a glycidyloxy group, an epoxy group, a mercapto group, a hydroxyl group, an amino group, Or it is an organic group containing an isocyanate group. M represents the valence of M ¹ , n represents an integer of 0 to m, s is 0 or 1,
t represents an integer of 0 to m. Further, n + t ≠ 0, and 1 ≦ n + t + s ≦ m.
When a plurality of R ¹ , R ² and X ¹ are present, each R ¹ , R ² and X ¹ may be the same or different. )   The said process (D1) is a process of performing at least 1 sort (s) of processing selected from the group which consists of a humidity control process, a boil process, and a retort process to a shaping | molding laminated body (C1). A method for producing the gas barrier molded laminate as described.   The process (D2) is a process of applying at least one kind of process selected from the group consisting of a humidity control process, a boil process, and a retort process to the molded laminate (B2). A method for producing the gas barrier molded laminate as described.   The step (D3) includes a step of immersing the molded laminate (C3) in a liquid containing a polyvalent metal compound and drying, and a liquid containing the polyvalent metal compound in the layer (A3) of the molded laminate (C3). It is at least 1 sort (s) of process selected from the group which consists of the process of spraying and drying, The manufacturing method of the gas barrier property fabrication layered product according to claim 3 characterized by things.   The step (D4) is a step of applying at least one kind of treatment selected from the group consisting of humidity control treatment, boil treatment, and retort treatment to the molded laminate (C4). A method for producing the gas barrier molded laminate as described.   The weight ratio of the polycarboxylic acid polymer contained in the coating liquid (A) to the plasticizer is 99.5: 0.5 to 70:30, The manufacturing method of the gas-barrier molded laminated body of description.   The weight ratio of the polycarboxylic acid polymer contained in the coating liquid (A) to the hydrolysis condensate of at least one compound represented by the general formula (1) is 99.5: 0.5 to It is 40:60, The manufacturing method of the gas-barrier molded laminated body in any one of Claims 1-9 characterized by the above-mentioned.   The polycarboxylic acid polymer contained in the coating liquid (A) is a structural unit derived from at least one polymerizable monomer selected from acrylic acid, maleic acid, methacrylic acid, and itaconic acid. The method for producing a gas barrier molded laminate according to any one of claims 1 to 10, which is a (co) polymer containing or a mixture of the (co) polymer.   The plasticizer contained in the coating liquid (A) is at least one plasticizer selected from the group consisting of polyethylene glycol, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, starch and glycerin. The manufacturing method of the gas-barrier shaping | molding laminated body in any one of Claims 1-11.   The polyvalent metal compound contained in the layer (B1), (B2) or (B4) is a calcium compound or a zinc compound. , 11, 12. A method for producing a gas barrier molded laminate according to any one of claims 11 and 12.   The gas barrier molding laminate according to any one of claims 3, 7, 9, 10, 11, and 12, wherein in the step (D3), the polyvalent metal compound is a calcium compound or a zinc compound. Method.   The shape of the gas barrier molding laminate is any form selected from the group consisting of a film, a sheet, a bottle, a cup, a tray, a container, a tank, and a tire. A method for producing a gas barrier molded laminate according to claim 1.   A gas barrier molded laminate produced by the method for producing a gas barrier molded laminate according to claim 1.