JP2020104288A - Laminate - Google Patents

Abstract

To provide a laminate which has extremely high gas barrier properties against water vapor, oxygen, hydrogen or the like, especially a laminate excellent in water resistance which exhibits high water vapor barrier properties even under high-humidity conditions.SOLUTION: The laminate is formed by laminating a resin layer (I) and a second layer (II). The second layer (II) is an inorganic oxide layer. The resin layer (I) comprises a composition which contains a compound A containing a specific structure having an isocyanate group, a compound B containing a specific structure having a hydroxyl group and a carboxy group, and a compound C having an aromatic ring or alicyclic structure and two or more epoxy groups. The molar ratio of epoxy groups to carboxy groups in the composition is 0.1-1.8.SELECTED DRAWING: Figure 1B

Description

The present invention relates to a laminate having excellent gas barrier properties.

Packaging materials used for packaging foods and beverages have strength, resistance to cracking, retort resistance, heat resistance, and gas barrier in order to protect the contents from various distribution, storage such as refrigeration, and treatment such as heat sterilization. Functions such as sex are required. Further, it is required to have a function such as excellent transparency so that the contents can be confirmed.
For reasons such as transparency, lightness, and economy, the use of plastic films and plastic containers has become the mainstream as packaging materials. The properties required of plastic films used for packaging foods, pharmaceuticals, cosmetics and the like include barrier properties against various gases, transparency, retort treatment resistance, impact resistance, flexibility, heat sealability and the like. Among these performances, a high gas barrier property against oxygen and water vapor is required for the purpose of maintaining the performance or properties of the contents. In particular, it is desired to exhibit a high gas barrier property even under high humidity conditions and conditions after retort treatment.

The gas barrier packaging material is configured by laminating each material layer such as a flexible polymer film layer serving as a base material, a gas barrier layer, and a flexible polymer film layer serving as a sealant layer.
Among these, vinylidene chloride has been used as a gas barrier material for forming the gas barrier layer in order to improve retort resistance and gas barrier properties against oxygen, water vapor and the like. However, vinylidene chloride has a problem that dioxin is generated during firing for disposal.
In addition, polyvinyl alcohol resins and ethylene-polyvinyl alcohol copolymers are also used as gas barrier materials. However, when these are used, there is a problem that the barrier property tends to decrease under high humidity, although the barrier property under high humidity is high.

Furthermore, it has been proposed to use a specific polyurethane resin as a gas barrier material (see, for example, Patent Documents 1 and 2). The gas barrier layer using the specific polyurethane resin described in Patent Documents 1 and 2 can exhibit gas barrier properties and transparency that are excellent to some extent. However, from the viewpoint of exhibiting a higher gas barrier property, particularly a high gas barrier property even under a high humidity condition, it cannot be said to be sufficiently satisfactory, and there is room for improvement.

JP, 2001-98047, A JP, 2006-143991, A

Therefore, an object of the present invention is to provide a laminate having an extremely high gas barrier property against water vapor, oxygen, hydrogen, etc., particularly a laminate excellent in water resistance, which exhibits a high water vapor barrier property even under high humidity conditions. And

As a result of intensive studies to solve the above-mentioned problems, the present inventors have made a resin layer (I) composed of a composition having a specific compound and a second layer (II) composed of an inorganic oxide layer. The inventors have found that a laminated body formed by laminating can solve the above problems, and have completed the present invention.

（式（１）において、Ｘ_１は芳香環又は脂環構造を表し、ｎ１及びｎ２はそれぞれ独立して０〜３の整数を表す。）

（式（２）において、Ｒ_１は水素原子又は炭素数１〜３の炭化水素基又はカルボニル基を表し、ｍ１〜ｍ３はそれぞれ独立して０〜３の整数を表す。） That is, the present invention includes the following aspects.
[1] A laminate in which a resin layer (I) and a second layer (II) are laminated,
The second layer (II) is an inorganic oxide layer,
The resin layer (I) has a compound A represented by the following formula (1), a compound B represented by the following formula (2), and a compound having an aromatic ring or alicyclic structure and two or more epoxy groups. A laminated body comprising a composition containing C and a molar ratio of epoxy groups to carboxy groups in the composition is 0.1 to 1.8.

(In the formula (1), X ₁ represents an aromatic ring or an alicyclic structure, and n1 and n2 each independently represent an integer of 0 to 3.)

(In the formula (2), R ₁ represents a hydrogen atom, a hydrocarbon group having 1 to 3 carbon atoms or a carbonyl group, and m 1 to m 3 each independently represent an integer of 0 to 3.)

（式（３）において、Ｘ_２は芳香環又は脂環構造を表し、ｎ３は２〜６の整数を表し、Ｒ_２はそれぞれ独立して下記式（４）で表される基を表す。

（Ｙ_１及びＹ_３はそれぞれ独立して２価の炭化水素基又は酸素原子を表し、Ｙ_２は３価の炭化水素基又は窒素原子を表し、ｎ４及びｎ６はそれぞれ独立して０〜３の整数を表し、ｎ５は０又は１であって、ｎ５が０の時ｎ７は１であって、ｎ５が１の時ｎ７は２を表す。）） [2] The laminate according to [1], wherein the compound C has a structure represented by the following formula (3).

(In formula (3), X ₂ represents an aromatic ring or an alicyclic structure, n 3 represents an integer of 2 to 6, and R ₂ independently represents a group represented by the following formula (4).

(Y ₁ and Y ₃ each independently represent a divalent hydrocarbon group or an oxygen atom, Y ₂ represents a trivalent hydrocarbon group or a nitrogen atom, and n4 and n6 are each independently 0 to 3 It represents an integer, n5 is 0 or 1, n7 is 1 when n5 is 0, and n7 is 2 when n5 is 1.))

[3] The laminate according to the above [1] or [2], wherein the compound C is an alicyclic epoxy compound.

[4] The laminate according to any one of [1] to [3], wherein X _{1 of the} formula (1) is a benzene ring or a naphthalene ring.

[5] The laminate according to any one of [1] to [4], wherein m3 of the formula (2) is 0.

[6] The laminate according to any one of [2] to [5], wherein X _{2 in the} formula (3) is a benzene ring, a naphthalene ring or a cycloalkane.

[7] The laminate according to any one of [3] to [6], wherein the alicyclic epoxy group of the alicyclic epoxy compound is a cyclopentene oxide group or a cyclohexene oxide group.

[8] The laminate according to any one of [1] to [7], wherein the resin layer (I) is a cured product layer obtained by curing the composition.

[9] The laminated body according to any one of the above [1] to [8], wherein the laminated body further has a third layer (III).

[10] The laminate according to any one of [1] to [9], wherein the inorganic oxide layer is an inorganic oxide layer formed by a chemical vapor deposition method (CVD method).

[11] The laminated body according to any one of the above [1] to [10], wherein the laminated body is a film.

（式（１）において、Ｘ_１は芳香環又は脂環構造を表し、ｎ１及びｎ２はそれぞれ独立して０〜３の整数を表す。）

（式（２）において、Ｒ_１は水素原子又は炭素数１〜３の炭化水素基又はカルボニル基を表し、ｍ１〜ｍ３はそれぞれ独立して０〜３の整数を表す。） [12] A method for producing a laminate in which a resin layer (I) and a second layer (II) are laminated,
The second layer (II) of the inorganic oxide layer,
Resin P of a reaction product obtained by reacting a compound A represented by the following formula (1) with a compound B represented by the following formula (2), an aromatic ring or alicyclic structure, and two or more epoxy groups A method for producing a laminate, comprising: laminating the resin layer (I), which is formed by using a composition containing the compound C having:

(In the formula (1), X ₁ represents an aromatic ring or an alicyclic structure, and n1 and n2 each independently represent an integer of 0 to 3.)

(In the formula (2), R ₁ represents a hydrogen atom, a hydrocarbon group having 1 to 3 carbon atoms or a carbonyl group, and m 1 to m 3 each independently represent an integer of 0 to 3.)

[13] A gas barrier material containing the laminate according to any one of [1] to [11].

[14] A packaging material containing the laminate according to any one of [1] to [11].

According to the present invention, it is possible to provide a laminate having an extremely high gas barrier property against water vapor, oxygen, hydrogen or the like, particularly a laminate excellent in water resistance that exhibits a high water vapor barrier property even under high humidity conditions. ..

It is an outline sectional view showing one mode of layer composition of a layered product of the present invention. It is a schematic sectional drawing which shows another aspect of the laminated constitution of the laminated body of this invention. It is a schematic sectional drawing which shows another aspect of the laminated constitution of the laminated body of this invention. It is a schematic sectional drawing which shows another aspect of the laminated constitution of the laminated body of this invention. It is a schematic sectional drawing which shows another aspect of the laminated constitution of the laminated body of this invention. It is a schematic sectional drawing which shows another aspect of the laminated constitution of the laminated body of this invention.

Hereinafter, the laminated body of the present invention will be described in detail, but the description of the constituent elements described below is an example as one embodiment of the present invention, and is not limited to these contents.

(Laminate)
The laminate of the present invention is a laminate in which the resin layer (I) and the second layer (II) are laminated.
The laminate of the present invention has at least the resin layer (I) and the second layer (II), and more preferably has the third layer (III).

（式（１）において、Ｘ_１は芳香環又は脂環構造を表し、ｎ１及びｎ２はそれぞれ独立して０〜３の整数を表す。）

（式（２）において、Ｒ_１は水素原子又は炭素数１〜３の炭化水素基又はカルボニル基を表し、ｍ１〜ｍ３はそれぞれ独立して０〜３の整数を表す。） <Resin layer (I)>
The resin layer (I) includes a compound A represented by the following formula (1), a compound B represented by the following formula (2), and a compound C having an aromatic ring or alicyclic structure and two or more epoxy groups. And a molar ratio of epoxy groups to carboxy groups in the composition is 0.1 to 1.8.

(In the formula (1), X ₁ represents an aromatic ring or an alicyclic structure, and n1 and n2 each independently represent an integer of 0 to 3.)

(In the formula (2), R ₁ represents a hydrogen atom, a hydrocarbon group having 1 to 3 carbon atoms or a carbonyl group, and m 1 to m 3 each independently represent an integer of 0 to 3.)

<<Compound A>>
The compound A is a compound having an isocyanate group represented by the above formula (1). In the compound A, X ₁ represents an aromatic ring or an alicyclic structure. By having an aromatic ring or alicyclic structure, high barrier properties can be exhibited.

The aromatic ring structure is appropriately selected depending on the intended purpose without any limitation, and examples thereof include aromatic rings having 6 to 18 carbon atoms. More specifically, examples thereof include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring.
The aromatic ring may be substituted with at least one fluorine atom. Examples of the aromatic ring substituted with at least one fluorine atom include a perfluorophenyl group.
The alicyclic structure is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alicyclic structures having 3 to 20 carbon atoms, which may be monocyclic or condensed rings. Examples of monocyclic cycloalkanes include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane and cyclododecane. Examples of monocyclic cycloalkenes include cyclopropene, cyclobutene, cyclopropene, cyclohexene, cycloheptene, cyclooctene and the like. Examples of the condensed ring include bicycloundecane, decahydronaphthalene, norbornene, norbornadiene and the like. In addition, examples of the polycyclic compound include cubane, basketane, hausan and the like.
Further, X ₁ may have a ring structure in which an aromatic ring structure and an alicyclic structure are combined.

In compound A, X ₁ is preferably a benzene ring or a naphthalene ring. Further, it is preferable that n1 and n2 are independently 0 to 1.

Compound A is more preferably a compound having the following structure.

<<Compound B>>
The compound B is a diol compound represented by the above formula (2) and having a hydroxyl group and a carboxy group. By having a carboxy group, it reacts with the compound C described later to form a crosslinked structure, and can exhibit high gas barrier properties under high humidity.

In compound B, m3 is preferably 0, and R ₁ is preferably a hydrocarbon group having 1 to 3 carbon atoms.

More preferably, compound B is dimethylolpropionic acid or dimethylolbutanoic acid.

<<Compound C>>
The compound C is a compound having an aromatic ring or alicyclic structure and two or more epoxy groups. By containing the compound C, a high barrier property is exhibited due to the aromatic ring or alicyclic structure in the compound C. Further, the epoxy group reacts with the carboxy group of the compound B to form a crosslinked structure, which can exhibit a high gas barrier property under high humidity.

As the compound C, an alicyclic epoxy compound or a compound having a structure represented by the following formula (3) is more preferable.

(In the formula (3), _{X 2} represents an aromatic ring or alicyclic structure, n3 is an integer of 2 to 6, a group represented by the following formula _{R 2} are each independently (4).)

(Y ₁ and Y ₃ each independently represent a divalent hydrocarbon group or an oxygen atom, Y ₂ represents a trivalent hydrocarbon group or a nitrogen atom, and n4 and n6 are each independently 0 to 3 Represents an integer, n5 is 0 or 1, n7 is 1 when n5 is 0, and n7 is 2 when n5 is 1.)

When the compound C has a structure represented by the formula (3), examples of the aromatic ring or alicyclic structure for X ₂ include the same structures as the aromatic ring or alicyclic structure for the compound A. Among them, X ₂ is more preferably a benzene ring, a naphthalene ring or a cycloalkane.

When compound C has a structure represented by formula (3), it is more preferable that Y ₁ is an oxygen atom.

When the compound C has a structure represented by the formula (3), it is particularly preferably a compound having the following structure.

Further, when the compound C is an alicyclic epoxy compound, the alicyclic epoxy group of the alicyclic epoxy compound is more preferably a cyclopentene oxide group or a cyclohexene oxide group.
When the compound C is an alicyclic epoxy compound, it is particularly preferably a compound having the following structure.

<< composition >>
One aspect of the composition forming the resin layer (I) is a composition containing the compound A, the compound B, and the compound C. When the molar ratio of the epoxy group to the carboxy group in the composition is 0.1 or more, the problem of poor curability and poor moldability when the resin layer is cured can be effectively prevented. On the other hand, when the molar ratio is 1.8 or less, the gas barrier property under high humidity can be sufficiently ensured.
Therefore, the molar ratio of the epoxy group to the carboxy group in the composition is preferably 0.1 to 1.8, more preferably 0.1 to 1.5.

Another embodiment of the composition forming the resin layer (I) is a composition containing a resin P, which is a reaction product of the compound A and the compound B, and the compound C.
Also in this embodiment, the molar ratio of the epoxy group to the carboxy group in the composition is preferably 0.1 to 1.8, more preferably 0.1 to 1.5.
When the compound P is first synthesized by reacting the compound A with the compound B, and then the resin P and the compound C are mixed, although the number of steps is increased, a side reaction can be effectively prevented and the resin P can be effectively prevented. The resin layer (I) composed of the composition containing the compound C and the compound C is cured to finally obtain a cured product layer having improved layer uniformity.

From the viewpoint of gas barrier properties, the compound A is preferably contained in an amount of 25 to 50 mass% with respect to the total solid content of the resin composition forming the resin layer (I).
From the viewpoint of gas barrier properties, the compound B is preferably contained in an amount of 20 to 40 mass% with respect to the total solid content of the resin composition forming the resin layer (I).
From the viewpoint of gas barrier properties, the above compound C is preferably contained in an amount of 10 to 40% by mass based on the total solid content of the resin composition constituting the resin layer (I).

The mixing ratio of the resin P, which is a reaction product of the compound A and the compound B, and the compound C is not particularly limited, but is preferably 55:45 to 90:10 by mass ratio, for example.
The reaction conditions for obtaining the resin P by reacting the compound A and the compound B are appropriately selected depending on the intended purpose without any limitation, but, for example, the reaction is performed at 40 to 120° C. for 1 to 24 hours. Good.

The composition forming the resin layer (I) may contain, in addition to the compound A, the compound B, and the compound C, other components, if necessary.
The other components are appropriately selected depending on the intended purpose without any limitation, and examples thereof include fillers, solvents, various additives, and curing agents.

<<<<Filler>>>>
The composition may contain a filler. The filler is not particularly limited and may be appropriately selected depending on the purpose, but examples thereof include an inorganic filler and an organic filler. The shape of the filler is not particularly limited, and examples thereof include various shapes such as spherical shape, granular shape, rod shape, needle shape, fiber shape, plate shape, and woven/nonwoven cloth shape. The aspect ratio of the filler is not particularly limited, either high or low.

In order to impart further barrier properties to the resin layer (I), the composition may contain a filler for improving the barrier properties. Examples thereof include layered inorganic compounds and compounds having an oxygen scavenging function.

The layered inorganic compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include hydrous silicates (phyllosilicate minerals, etc.), kaolinite group clay minerals (halloysite, kaolinite, enderite). , Dickite, Nacrite, etc.), Antigorite group clay minerals (Antigolite, chrysotile, etc.), Smectite group clay minerals (Montmorillonite, Beidellite, Nontronite, Saponite, Hectorite, Sawconite, Stevensite, etc.), Vermiculite group clay Minerals (vermiculite etc.), mica or mica group clay minerals (mica such as muscovite and phlogopite, margarite, tetrasilylic mica, teniolite etc.) and the like can be mentioned. These minerals may be natural clay minerals or synthetic clay minerals. The layered inorganic compound may be used alone or in combination of two or more kinds.

When the layered clay mineral is contained, the content of the layered clay mineral in the composition is preferably 5 to 60% by mass, more preferably 5 to 50% by mass.

The compound having an oxygen scavenging function is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include oxygen such as hindered phenols, vitamin C, vitamin E, organic phosphorus compounds, gallic acid and pyrogallol. Examples thereof include low molecular weight organic compounds that react with or transition metal compounds such as cobalt, manganese, nickel, iron and copper.

<<<<solvent>>>>
The composition may contain a solvent. The solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include organic solvents. The organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose, for example, methyl ethyl ketone, acetone, ethyl acetate, butyl acetate, toluene, dimethylformamide, acetonitrile, methyl isobutyl ketone, methanol, ethanol, methoxy. Propanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate and the like can be mentioned. The type and amount of the solvent can be appropriately selected depending on the purpose of use.

<<< Various additives>>>
The composition may contain various additives. Various additives can be contained in the composition as long as the effects of the present invention are not impaired. The additive is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include various resins, reactive compounds, catalysts, polymerization initiators, stabilizers (antioxidants, heat stabilizers, and ultraviolet absorbers). Agents, etc.), plasticizers, waxes, surfactants, stabilizers, flow regulators, antistatic agents, lubricants, antiblocking agents, colorants, crystal nucleating agents, coupling agents, dyes, leveling agents, rheology control agents, Examples thereof include ultraviolet absorbers, hygroscopic agents, tackifiers, and the like.

<<<Curing agent>>>>
The composition may contain a curing agent. The curing agent is not particularly limited and can be appropriately selected depending on the purpose. For example, when the composition contains the compound C having an epoxy group, examples of the curing agent include amine curing agents, amide curing agents, acid anhydride curing agents, phenol curing agents, and active ester curing agents. Examples of the curing agent include a curing agent, a carboxyl group-containing curing agent, and a thiol-based curing agent.

More specifically, as the amine curing agent, for example, diaminodiphenylmethane, diaminodiphenylethane, diaminodiphenyl ether, diaminodiphenyl sulfone, orthophenylenediamine, metaphenylenediamine, paraphenylenediamine, metaxylenediamine, paraxylenediamine, diethyl. Examples thereof include toluenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, imidazole, BF3-amine complex, guanidine derivative and guanamine derivative.

Examples of the amide-based curing agent include dicyandiamide, a polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine, and the like.
Examples of the acid anhydride-based curing agent include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, hexahydrophthalic anhydride, Methyl hexahydrophthalic anhydride and the like can be mentioned.
Examples of the phenol-based curing agent include bisphenol A, bisphenol F, bisphenol S, resorcin, catechol, hydroquinone, fluorene bisphenol, 4,4′-biphenol, 4,4′,4″-trihydroxytriphenylmethane, naphthalenediol. , 1,1,2,2-Tetrakis(4-hydroxyphenyl)ethane, calixarene, phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition resin, phenol aralkyl resin (Zylok resin), polyhydric phenol novolac resin represented by resorcinol novolac resin and formaldehyde, naphthol aralkyl resin, trimethylolmethane resin, tetraphenylolethane resin, naphthol novolac resin, naphthol-phenol Co-condensed novolac resin, naphthol-cresol co-contracted novolac resin, biphenyl modified phenol resin (polyhydric phenol compound in which phenol nucleus is linked by bismethylene group), biphenyl modified naphthol resin (polyvalent naphthol in which phenol nucleus is linked by bismethylene group) Compound), aminotriazine-modified phenol resin (polyhydric phenol compound in which phenol nucleus is linked with melamine, benzoguanamine, etc.) or alkoxy group-containing aromatic ring-modified novolak resin (formaldehyde in which phenol nucleus and alkoxy group-containing aromatic ring are linked) And a polyhydric phenol compound such as a (hydric phenol compound).
The curing agents may be used alone or in combination of two or more.

Further, a curing accelerator can also be used. The curing accelerator is not particularly limited and may be appropriately selected depending on the purpose. For example, various compounds that accelerate the curing reaction of the epoxy resin may be used. More specifically, examples thereof include phosphorus compounds, tertiary amine compounds, imidazole compounds, organic acid metal salts, Lewis acids, amine complex salts and the like. Among these, it is preferable to use an imidazole compound, a phosphorus compound, and a tertiary amine compound. In particular, from the viewpoint of excellent curability, heat resistance, electrical characteristics, moisture resistance reliability, etc., triphenylphosphine for phosphorus compounds and 1,8-diazabicyclo-[5.4.0]-undecene (for tertiary amine compounds) It is preferred to use DBU).

<<Formation of Cured Product Layer>>
The composition forming the resin layer (I) can be cured.
The curing method is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a known and commonly used curing method may be used. For example, heat curing or heat radical curing may be used.
When the composition is cured, the composition containing the compound A, the compound B and the compound C may be cured, or after the resin P in which the compound A and the compound B are reacted is produced, it is reacted with the compound C. You may cure by making it do. When the compound P is previously synthesized by reacting the compound A with the compound B, the number of steps is increased, but side reactions are less likely to occur, and thus the uniformity of the final cured product can be improved.
Moreover, when hardening, you may use the above-mentioned hardening|curing agent and hardening accelerator.

The thickness of the cured product layer is not particularly limited and may be appropriately selected depending on the purpose. For example, the thickness of the cured product layer of the resin layer (I) after curing the composition is It is practically preferable that the thickness is smaller than that of the base material which is the third layer (III) described in (1). Therefore, the thickness of the cured product layer of the resin layer (I) is preferably 10 nm to 10 μm, for example. In consideration of the drying speed when obtaining the cured product layer and the fact that a cured product layer having a uniform thickness is obtained during drying, the thickness of the cured product layer of the resin layer (I) is more preferably 50 nm to 8 μm, and 100 nm. ˜5 μm is more preferred.
The method for measuring the layer thickness is not particularly limited and can be appropriately selected according to the purpose using a commonly known method, and examples thereof include film thickness measurement with a micrometer.

A molded product can be produced by molding the above composition.
The molding method is not particularly limited and can be appropriately selected according to the purpose. The shape of the molded body is not particularly limited and may be appropriately selected depending on the intended purpose, and examples thereof include a plate shape, a sheet shape, and a film shape. Further, the molded body may have a three-dimensional shape, and may be applied on the base material which is the third layer (III) described below or on the second layer (II).
In the case of producing a plate-shaped or sheet-shaped molded body, examples of the molding method include an extrusion molding method, a plane pressing method, a profile extrusion molding method, a blow molding method, a compression molding method, a vacuum molding method, and an injection molding method. Can be mentioned. When producing a film-shaped molded product, for example, a melt extrusion method, a solution casting method, an inflation film molding method, a cast molding method, an extrusion lamination molding method, a calendar molding method, a sheet molding method, a fiber molding method, a blow molding method. Methods, injection molding methods, rotational molding methods, coating molding methods and the like.
When the composition is a composition that cures with heat or active energy rays, the composition may be molded using various curing methods using heat or active energy rays to produce a molded body.
When the composition is liquid, the composition may be molded by a coating method to produce a molded product. The coating method is not particularly limited and may be appropriately selected depending on the intended purpose, for example, spray method, spin coating method, dip method, roll coating method, blade coating method, doctor roll method, doctor blade method. , A curtain coating method, a slit coating method, a screen printing method, an inkjet method, a dispensing method and the like.

<Second layer (II)>
The second layer (II) is an inorganic oxide layer.
By stacking the resin layer (I) and the second layer (II) made of an inorganic oxide layer, it is possible to obtain a laminate capable of realizing higher gas barrier properties.
In the present invention, a film made of an inorganic oxide can be formed on the film formation target (i). Here, the film formation target (i) refers to the base material which is the third layer (III) described below and/or the resin layer (I). When the laminate has various other functional layers other than the base material as the third layer (III) described below, the film formation target (i) means that the various other functional layers are added. It may also refer to the substrate and/or the resin layer (I).

The type of inorganic oxide is not particularly limited and may be appropriately selected depending on the intended purpose, and examples thereof include silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, and zinc oxide. These may be used alone or in combination of two or more.
The shape of the inorganic oxide layer is not particularly limited and may be appropriately selected depending on the intended purpose, and examples thereof include a plate shape, a sheet shape, and a film shape.

<<Method of forming inorganic oxide layer>>
The method for molding the inorganic oxide layer is not particularly limited and can be appropriately selected depending on the purpose. For example, the inorganic oxide layer can be laminated on the film formation target (i) by a coating method or a plating method.
When the inorganic oxide layer is formed by the coating method, the inorganic oxide layer can be formed by applying and curing the coating liquid of the inorganic oxide.
The coating method is not particularly limited and may be appropriately selected depending on the intended purpose, for example, spray method, spin coating method, dip method, roll coating method, blade coating method, doctor roll method, doctor blade method. The curtain coating method, the slit coating method, the screen printing method, the ink jet method and the like can be mentioned.

The coating liquid material of the inorganic oxide may be particles of the inorganic oxide, or a metal alkoxide compound which becomes an inorganic oxide by hydrolysis or a hydrolysis-condensation product thereof.
When a coating liquid of a metal alkoxide compound is used, it is more preferable to use a curable organopolysiloxane and a coating liquid that is cured by heat or active energy rays such as electron beams and ultraviolet rays. When the curable organopolysiloxane is used, the crosslink density is increased by three-dimensionally crosslinking, and a cured organopolysiloxane layer exhibiting high abrasion resistance can be obtained.

Examples of the metal alkoxide compound or the hydrolytic condensate thereof include a silane compound having a silanol group and/or a hydrolyzable silyl group, and a hydrolytic condensate thereof. Specific examples thereof include known and commonly used silane compounds, such as methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, and iso-butyltrimethoxy. Various organotrialkoxysilanes such as silane and cyclohexyltrimethoxysilane; Various diorganodialkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-butoxysilane, diethyldimethoxysilane, and methylcyclohexyldimethoxysilane. Examples: chlorosilanes such as methyltrichlorosilane, ethyltrichlorosilane, vinyltrichlorosilane, dimethyldichlorosilane, diethyldichlorosilane and the like. Among them, organotrialkoxysilanes and diorganodialkoxysilanes, which can easily undergo hydrolysis reaction and can easily remove by-products after the reaction, are preferable.

Further, the inorganic oxide layer may be formed by a plating method.
The plating method is appropriately selected depending on the intended purpose without any limitation, and examples thereof include a dry plating method and a wet plating method.
Examples of the dry plating method include physical vapor deposition (PVD) such as vacuum deposition, sputtering, and ion plating, or chemical vapor deposition (CVD). On the other hand, examples of the wet plating method include an electroless plating method.
Among the plating methods, the dry plating method is preferable, and the plating method by chemical vapor deposition (CVD) is more preferable.
According to the chemical vapor deposition method (particularly the plasma chemical vapor deposition method (plasma CVD method)), an inorganic oxide layer having high denseness and high wear resistance can be obtained.

Hard materials that may be used as the plasma CVD coating layer include SiO ₂ , TiO ₂ , ZnO, Fe ₂ O ₃ , V ₂ O ₅ , SnO ₂ , PbO, Sb ₂ O _{3 and the} like. If it is desired to produce a transparent _laminate, SiC, SiO 2, ZnO is preferred, SiO ₂ is more preferable.

Examples of the silicon compound that is a raw material of the silicon oxide layer obtained by the plasma CVD method include silane, tetramethoxysilane, tetraethoxysilane (TEOS), tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, and the like. Tetra t-butoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltriethoxysilane, (3,3,3-trifluoropropyl)tri Methoxysilane, hexamethyldisiloxane (HMDSO), bis(dimethylamino)dimethylsilane, bis(dimethylamino)methylvinylsilane, bis(ethylamino)dimethylsilane, N,O-bis(trimethylsilyl)acetamide, bis(trimethylsilyl)carbodiimide , Diethylaminotrimethylsilane, dimethylaminodimethylsilane, hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, nonamethyltrisilazane, octamethylcyclotetrasilazane, tetrakisdimethylaminosilane, tetraisocyanatosilane, tetramethyldisilazane , Tris(dimethylamino)silane, triethoxyfluorosilane, allyldimethylsilane, allyltrimethylsilane, benzyltrimethylsilane, bis(trimethylsilyl)acetylene, 1,4-bistrimethylsilyl-1,3-butadiyne, di-t-butylsilane, 1,3-disilabutane, bis(trimethylsilyl)methane, cyclopentadienyltrimethylsilane, phenyldimethylsilane, phenyltrimethylsilane, propargyltrimethylsilane, tetramethylsilane, trimethylsilylacetylene, 1-(trimethylsilyl)-1-propyne, tris( Examples include trimethylsilyl)methane, tris(trimethylsilyl)silane, vinyltrimethylsilane, hexamethyldisilane, octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, hexamethylcyclotetrasiloxane, and M silicate 51.

It is advisable to mix a reactive gas composed of a raw material gas composed of a silicon compound and a decomposed gas composed of oxygen with a discharge gas which is likely to be in a plasma state, and to supply the gas to the plasma discharge generator. As such a discharge gas, oxygen gas, nitrogen gas, and/or an atom of Group 18 of the periodic table, specifically, for example, helium, neon, argon, krypton, xenon, radon, or the like is used. Among these, oxygen, nitrogen, helium and argon are preferably used.

The thickness of the inorganic oxide layer according to the present invention is not particularly limited and may be appropriately selected depending on the purpose, but is preferably 1 to 100 nm, for example. It is more preferably 2 to 50 nm and even more preferably 3 to 30 nm. Particularly preferably, it is 5 to 20 nm, and particularly preferably 5 to 15 nm. When the thickness of the inorganic oxide layer is 1 nm or more, a film with few defects can be formed. On the other hand, when the thickness is 100 nm or less, the flexibility of the film is sufficient, so that a laminate that is hard to break can be obtained.
The method for measuring the film thickness of the formed inorganic oxide layer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include film thickness measurement by spectroscopic ellipsometry using an ellipsometer.

<Third layer (III)>
The laminated body of the present invention may further have a third layer (III).
The laminate of the present invention preferably further has a third layer (III) in addition to the second layer (II) including the resin layer (I) and the inorganic oxide layer.
The third layer (III) is not particularly limited, and examples thereof include a base material functioning as a support for the laminate, and various functional layers useful for maintaining or improving the gas barrier function of the laminate of the present invention. To be

<<Substrate>>
The base material effectively functions as a support for a laminate having the resin layer (I) and the second layer (II) including the inorganic oxide layer.
The material of the base material is not particularly limited and may be appropriately selected according to the purpose. For example, wood, metal and metal oxide, plastic, paper, cloth, ceramic, rubber, silicon, modified silicon, or the like. Are listed. It may be a substrate obtained by joining different materials.
The type of plastic is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polylactic acid (PLA); polyethylene, Polyolefin resin such as polypropylene; cycloolefin resin such as cycloolefin; polystyrene resin; polyamide resin such as nylon 6, nylon 11, nylon 12, poly-p-xylylene adipamide (MXD6 nylon); polycarbonate resin; polyacrylonitrile Resin; ABS resin; Polytetrafluoroethylene resin; Polyimide resin; Polyphenylene sulfide resin; Polyamideimide resin; Polyethersulfone resin; Multi-layered products thereof (for example, nylon 6/MXD6/nylon 6, nylon 6/ethylene-vinyl alcohol) Examples thereof include a copolymer/nylon 6) and a mixture. Among them, those having mechanical strength or dimensional stability are preferable. Among them, those having mechanical strength or dimensional stability are preferable.

The shape of the base material is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a flat plate, a sheet shape, a film shape, or an object having a three-dimensional shape on the whole surface or a part thereof, or on the whole surface. Alternatively, it may have an arbitrary shape such as one having a part of curvature according to the purpose.
When the substrate is a plastic substrate, the plastic substrate is a molded article of plastic. The shape of the molded body is not limited, and molded bodies of various shapes can be used as the base material. For example, a plate, a sheet, a film, or a material having a three-dimensional shape on the whole surface or a part thereof, a material having a curvature on the whole surface or a part thereof, and the like can be given. Moreover, among these, a non-stretched film or a stretched film is more preferable.
The hardness of the base material is not particularly limited and can be appropriately selected according to the purpose.

When the substrate is a film, examples of the molding method include an extrusion method, a cast molding method, a T-die method, a cutting method and an inflation method. For these films, a plastic molded body formed by forming a single layer or a multilayer film can also be used as a substrate.
The thickness of the substrate is not particularly limited and may be appropriately selected depending on the purpose. For example, when the substrate is a film, it is preferably 1 to 300 μm. The thickness is more preferably 3 to 250 μm, further preferably 8 to 125 μm, and particularly preferably 12 to 75 μm.
When the thickness of the film-shaped substrate is 1 μm or more, there is no problem in strength and it can be used. On the other hand, when the thickness of the base material is 300 μm or less, bending deformation and winding of the obtained laminate are easy, which is preferable.

<<Various functional layers>>
The laminate of the present invention is a laminate having a resin layer (I) and a second layer (II) composed of an inorganic oxide layer, and preferably having a base material. It may have a third layer (III) composed of various functional layers such as a cover layer, an adhesive layer and the like.
Further, the laminate of the present invention may have various barrier function layers such as publicly known or commercially available gas barrier layers or light shielding layers.

<Layer structure of laminated body>
FIG. 1A is a schematic cross-sectional view showing one embodiment of the layer structure of the laminate of the present invention. FIG. 1B is a schematic cross-sectional view showing another aspect of the layer structure of the laminate of the invention.
As shown in FIGS. 1A and 1B, the first embodiment of the laminate of the present invention has 32 resin layers (I) and 33 second layer (II) inorganic oxide layers. , And a laminate having 31 base materials.
When the laminate of the present invention has 31 base materials, the 31 base material is on either side of the laminate composed of 32 resin layers (I) and 33 inorganic oxide layers. It may be arranged.
The stacking order of the base material of 31, the resin layer (I) of 32, and the inorganic oxide layer of 33 is appropriately selected according to the purpose.
For example, as shown in FIG. 1A, a laminated body in which a base material 31, a resin layer (I) 32, and an inorganic oxide layer 33 are laminated in this order may be used. Alternatively, as shown in FIG. 1B, it may be a laminated body in which a base material 31, an inorganic oxide layer 33, and a resin layer (I) 32 are laminated in this order.
In addition, at least one of the resin layer (I) 32 and the inorganic oxide layer 33 may be formed in multiple layers in the laminate. For example, as shown in FIG. 2A, the resin layer (I) 32 may be further laminated on a laminate of the base material 31, the resin layer (I) 32, and the inorganic oxide layer 33. Further, the resin layers (I) 32 and the inorganic oxide layers 33 may be laminated alternately to form a multilayer. For example, as shown in FIG. 2B, the inorganic oxide layer 33 may be further laminated on the base material 31, the resin layer (I) 32, the inorganic oxide layer 33, and the resin layer (I) 32. The resin layer (I) 32 and the inorganic oxide layer 33 may be further laminated on the laminated body of FIG. 2B, and the number of laminated resin layers (I) and inorganic oxide layers is appropriately selected according to the purpose. be able to.
The resin layer (I) 32 and the inorganic oxide layer 33 may be appropriately laminated on the laminate shown in FIG. 1B depending on the purpose. For example, as shown in FIG. 3A, the inorganic oxide layer 33 may be further laminated on a laminate of the base material 31, the inorganic oxide layer 33, and the resin layer (I) 32. Further, the resin layer (I) 32 and the inorganic oxide layer 33 may be laminated alternately to form a multilayer. For example, as shown in FIG. 3B, the resin layer (I) 32 may be further laminated on the base material 31, the inorganic oxide layer 33, the resin layer (I) 32, and the inorganic oxide layer 33. The inorganic oxide layer 33 and the resin layer (I) 32 may be further laminated on the laminated body of FIG. 3B, and the number of laminated resin layers (I) and inorganic oxide layers is appropriately selected according to the purpose. be able to.

Further, the inorganic oxide layer 33 and/or the resin layer (I) 32 may be formed on a plurality of surfaces of the base material. When the inorganic oxide layer 33 is formed on a plurality of surfaces of the base material or the laminate including the base material, the inorganic oxide layers 33 may be formed one by one on the surface on which the inorganic oxide layer is desired to be formed. Alternatively, the inorganic oxide layer 33 layer can be simultaneously formed on a plurality of surfaces by arranging the plurality of surfaces of the base material or the laminate including the base material in contact with the source gas in the reaction vessel. The laminate including the base material may have a plurality of resin layers (I) 32 formed thereon, or the resin layer (I) 32 may be formed on only one surface or a part of a plurality of surfaces. A plurality of layers may be formed on the entire surface of the base material in the same layer or in different layers with different layer configurations.
For example, in the case of a film-shaped laminate, the inorganic oxide layers 33 may be formed in various layer configurations as described above on both the front surface and the back surface of the film.

The film thickness of the entire layer of the laminate of the present invention is not particularly limited and may be appropriately set according to the purpose. For example, the film thickness of the base material, the resin layer (I) and the inorganic oxide layer. A laminate having a desired film thickness can be obtained by appropriately selecting the number of laminates.
For example, when a film-like laminate is prepared, the resin layer (I) of the present invention and the combination of the inorganic oxide layer can exhibit sufficient gas barrier properties even if the inorganic oxide layer is a thin layer, The entire laminate can be a thin film. For example, it is possible to obtain a good gas barrier property even if the film as a whole has a thickness of 100 μm or less.

<Method of manufacturing laminated body>
The laminate of the present invention is produced by laminating the resin layer (I) and the inorganic oxide layer which is the second layer (II).
As one embodiment of the laminate of the present invention, for example,
(A) a second layer (II) of the inorganic oxide layer,
(B) A resin P of a reaction product obtained by reacting the compound A represented by the formula (1) with the compound B represented by the formula (2), an aromatic ring or an alicyclic structure, and two or more. A resin layer (I) formed by using a composition containing the compound C having an epoxy group of
A method of manufacturing a laminated body in which

In the laminate of the present invention, the resin layer (I) is preferably laminated as a cured product layer obtained by curing the above composition.
Preferred embodiments of the method for producing a laminate of the present invention include, for example, a method for producing a laminate by laminating the resin layer (I) and the inorganic oxide layer on a substrate. Hereinafter, this manufacturing method will be described in detail.
The laminated body of the present invention can be obtained by laminating the above-mentioned molded body on the substrate and/or the inorganic oxide layer. Thereby, the resin layer (I) can be laminated on the base material and/or the inorganic oxide layer.
In the present specification, the “base material and/or the inorganic oxide layer” is also referred to as a film formation target (ii).
In order to stack the molded body on the film-forming target (ii), each molding method described above can be used.
When the molded body is laminated on the film-forming target (ii), there is no particular limitation whether the laminating step and the curing step are performed at the same time or any of the steps is performed first. For example, even if an uncured or semi-cured composition layer is laminated on the film formation target (ii) and then cured, a cured product layer obtained by completely curing the composition is laminated on the film formation target (ii). In any of the methods, the molded body can be laminated on the film formation target (ii), and a laminated body in which the resin layer (I) is laminated on the film formation target (ii) can be obtained.

On the other hand, in order to laminate the inorganic oxide layer on the substrate and/or the resin layer (I), for example, a coating method may be used as described in the section of <<Molding Method of Inorganic Oxide Layer>> above. Alternatively, by using the plating method, the inorganic oxide layer can be laminated on the film formation target (i). This makes it possible to obtain a laminate in which the inorganic oxide layer is laminated on the film formation target (i).

When the laminate of the present invention has various functional layers other than the base material as the third layer (III), the film-forming target (i) or the film-forming target ( With respect to ii), the resin layer (I) or the inorganic oxide layer can be laminated on the film-forming target by using the above-mentioned laminating method.

<Characteristics of laminated body>
The laminate of the present invention produced using the above-described lamination method is a cured product of a carboxyurethane resin obtained by curing a composition having the specific compound of the above compound A, the above compound B, and the above compound C. A layer and an inorganic oxide layer are laminated.
The laminate of the present invention is a laminate excellent in water resistance, which exhibits high water vapor barrier properties even under high humidity conditions, as shown in the following examples.
It is unknown how the cured product layer of carboxyurethane resin and the inorganic oxide layer are laminated to exert high water resistance. However, since the resin layer (I) obtained by curing the carboxyurethane resin has good adhesiveness with the inorganic oxide layer, a laminate including the resin layer (I) and the inorganic oxide layer is It is considered that a strong laminate having few voids can be obtained, and thus a laminate excellent in gas barrier property can be obtained.

(Gas barrier material, packaging material)
The gas barrier material of the present invention contains the above laminate of the present invention. The packaging material of the present invention contains the above-mentioned layered product of the present invention.
The laminate of the present invention has a very high gas barrier property against water vapor, oxygen, hydrogen, and the like. In particular, it exhibits a high water vapor barrier property even under high humidity conditions.
Therefore, the laminate of the present invention has excellent water resistance and can be applied to products in various fields requiring high gas barrier properties.
The laminate of the present invention can be suitably used as a gas barrier material. For example, it can be used for electric/electronic products such as packaging products, solar cells, organic light emitting diodes, wavelength conversion sheets, and display devices.
Moreover, the laminated body of this invention can be used especially suitably as a packaging material. For example, it can be suitably used as a packaging material for packaging products used in medicines, cosmetics, chemicals, foods and drinks and the like.

Hereinafter, the present invention will be described in more detail with reference to examples, but the scope of the present invention is not limited to these examples.

(Measurement method of water vapor transmission rate MVTR (g/(m ² ·day))
Using a water vapor transmission rate measuring device manufactured by Illinois, the water vapor transmission rate of the laminate was measured in an atmosphere of 40° C. and 90% RH in accordance with the conductivity method “ISO-15106-3”. ..

(Preparation example 1 of carboxyurethane resin solution)
[Preparation Example 1-1]
A glass flask equipped with a stirrer, a thermometer, a cooling tube, and a dropping device was charged with 90 parts by mass of DMPA (2,2-dimethylolpropanoic acid, manufactured by Tokyo Kasei), 54 parts by mass of methyl ethyl ketone as a solvent, and 81 parts by mass of tetrahydrofuran. , And stirred under a nitrogen stream. Next, 56 parts by mass of XDI (xylylene diisocyanate, trade name: Takenate 500, manufactured by Mitsui Chemicals) was charged, and the temperature was raised to 60°C. After stirring at the same temperature for 1 hour, the temperature was lowered to 40°C or lower, 56 parts by mass of XDI was further charged, and the temperature was raised to 60°C again. The reaction was continued until the disappearance of isocyanate groups was confirmed by infrared spectroscopy. Next, 148 parts by mass of methanol was added as a diluent solvent to obtain a polyurethane solution 1 containing 50% by mass of a urethane resin "DMPA/XDI" containing a carboxy group.

[Preparation Example 1-2]
10 parts by mass of the polyurethane solution 1 produced in Preparation Example 1-1, 1.83 parts by mass of 3′,4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (trade name: Celoxide 2021P, manufactured by Daicel) (Epoxy group is 1 equivalent to the carboxy group of "DMPA/XDI"), 0.07 parts by mass of triphenylphosphine (1% by mass relative to the total mass of urethane resin and epoxy resin), methanol as a curing catalyst. 16 parts by mass were mixed to prepare a coating liquid 1 having a nonvolatile content of 25% by mass.

(Comparative Urethane Resin (Urethane Resin Having No Carboxy Group) Solution Preparation Example 2)
[Comparative Preparation Example 2-1]
A glass flask equipped with a stirrer, a thermometer, a cooling tube, and a dropping device was charged with 40 parts by mass of NPG (neopentyl glycol, manufactured by Tokyo Kasei) and 62 parts by mass of methyl ethyl ketone as a solvent, and stirred under a nitrogen stream. Then, 17.8 parts by mass of TDI (toluene diisocyanate, trade name: Coronate T-80, manufactured by Tosoh Corporation) was charged, and the temperature was raised to 60°C. After stirring at the same temperature for 1 hour, the temperature was lowered to 40° C. or lower, 17.8 parts by mass of TDI was charged, and the temperature was raised to 60° C. again. After stirring at the same temperature for 1 hour, the temperature was lowered to 40° C. or lower, 17.8 parts by mass of TDI was further charged, and the temperature was raised to 60° C. again. The reaction was continued until the disappearance of isocyanate groups was confirmed by infrared spectroscopy. Next, 31 parts by mass of methyl ethyl ketone was added as a diluting solvent to obtain a comparative polyurethane solution 1 containing 50% by mass of the urethane resin "NPG/TDI".

[Comparative Preparation Example 2-2]
10 parts by mass of the comparative polyurethane solution 1 prepared in Comparative Preparation Example 2-1 and 10 parts by mass of methyl ethyl ketone were blended to prepare a comparative coating liquid 1 having a nonvolatile content of 25% by mass.

(Example 1)
The laminate shown in FIG. 1B was produced.
In the laminated body shown in FIG. 1B, as the base material 31 on which the inorganic oxide layer 33 is formed, a transparent film (barrier locks 1011HG, thickness 12 μm, which is obtained by vapor-depositing aluminum oxide on a PET (polyethylene terephthalate) film with a thickness of about 20 nm. Manufactured by Toray Industries, Inc.) was used.
On the vapor-deposited layer made of aluminum oxide formed on the PET film, the coating liquid 1 was applied as a resin layer (I) 32 with a bar coater #4, dried with a dryer, and then heated at 80° C. for 12 hours for curing. Then, the resin layer 1 was formed. The film thickness of the cured product layer of the resin layer 1 was 2 μm.

(Comparative Example 1)
In the laminated body shown in FIG. 1B, as the base material 31 on which the inorganic oxide layer 33 is formed, a transparent film (barrier locks 1011HG, thickness 12 μm, which is obtained by vapor-depositing aluminum oxide on a PET (polyethylene terephthalate) film with a thickness of about 20 nm. Manufactured by Toray Industries, Inc.) was used.
The resin layer 1 as the resin layer (I) 32 was not formed on the aluminum oxide vapor deposition layer as the inorganic oxide layer 33.

(Comparative example 2)
In the laminated body shown in FIG. 1B, as the base material 31 on which the inorganic oxide layer 33 is formed, a transparent film (barrier locks 1011HG, thickness 12 μm, which is obtained by vapor-depositing aluminum oxide on a PET (polyethylene terephthalate) film with a thickness of about 20 nm. Manufactured by Toray Industries, Inc.) was used.
On the vapor-deposited layer made of aluminum oxide formed on the PET film, the comparative coating solution 1 was applied as a resin layer (I) 32 with a bar coater #4 and dried with a dryer to form the resin layer 1. The film thickness of the cured product layer of the resin layer 1 was 2 μm.

The measurement results of the water vapor transmission rate MVTR (g/(m ² ·day) of the laminates of Example 1, Comparative Example 1 and Comparative Example 2 are shown in Table 1 below, where the low water vapor transmission rate MVTR was obtained. It is shown that the laminated body shown, that is, the laminated body which is impermeable to water vapor, has an effect of preventing the base material and contents from being deteriorated by water.

The laminate of Example 1 has a lower water vapor transmission rate MVTR than the laminates of Comparative Examples 1 and 2 and is a laminate excellent in water resistance, which prevents the base material and contents from being deteriorated by water. Was confirmed.
As shown in Examples, a laminate of the present invention obtained by laminating a cured product layer of a carboxyurethane resin obtained by curing a composition having a specific compound and an inorganic oxide layer has high humidity. A laminated body having excellent water resistance, which exhibits high water vapor barrier properties even under the conditions.

31 Base Material 32 Resin Layer (I)
33 Inorganic oxide layer of second layer (II)

Claims (14)

A laminated body in which a resin layer (I) and a second layer (II) are laminated,
The second layer (II) is an inorganic oxide layer,
The resin layer (I) has a compound A represented by the following formula (1), a compound B represented by the following formula (2), and a compound having an aromatic ring or alicyclic structure and two or more epoxy groups. A laminated body comprising a composition containing C and a molar ratio of an epoxy group to a carboxyl group in the composition is 0.1 to 1.8.

(In the formula (1), X ₁ represents an aromatic ring or an alicyclic structure, and n1 and n2 each independently represent an integer of 0 to 3.)

(In the formula (2), R ₁ represents a hydrogen atom, a hydrocarbon group having 1 to 3 carbon atoms or a carbonyl group, and m 1 to m 3 each independently represent an integer of 0 to 3.) The laminate according to claim 1, wherein the compound C has a structure represented by the following formula (3).

(In formula (3), X ₂ represents an aromatic ring or an alicyclic structure, n 3 represents an integer of 2 to 6, and R ₂ independently represents a group represented by the following formula (4).

(Y ₁ and Y ₃ each independently represent a divalent hydrocarbon group or an oxygen atom, Y ₂ represents a trivalent hydrocarbon group or a nitrogen atom, and n4 and n6 are each independently 0 to 3 It represents an integer, n5 is 0 or 1, n7 is 1 when n5 is 0, and n7 is 2 when n5 is 1.)) The laminate according to claim 1 or 2, wherein the compound C is an alicyclic epoxy compound. The laminate according to claim 1, wherein X _{1 in the} formula (1) is a benzene ring or a naphthalene ring. The layered product according to any one of claims 1 to 4, wherein m3 in the formula (2) is 0. The laminate according to any one of claims 2 to 5, wherein X _{2 in the} formula (3) is a benzene ring, a naphthalene ring or a cycloalkane. The laminate according to any one of claims 3 to 6, wherein the alicyclic epoxy group of the alicyclic epoxy compound is a cyclopentene oxide group or a cyclohexene oxide group. The laminate according to any one of claims 1 to 7, wherein the resin layer (I) is a cured product layer obtained by curing the composition. The laminated body according to any one of claims 1 to 8, wherein the laminated body further has a third layer (III). The laminate according to any one of claims 1 to 9, wherein the inorganic oxide layer is an inorganic oxide layer formed by a chemical vapor deposition method (CVD method). The laminate according to any one of claims 1 to 10, wherein the laminate is a film. A method for producing a laminate, in which a resin layer (I) and a second layer (II) are laminated,
The second layer (II) of the inorganic oxide layer,
Resin P of a reaction product obtained by reacting a compound A represented by the following formula (1) with a compound B represented by the following formula (2), an aromatic ring or alicyclic structure, and two or more epoxy groups A method for producing a laminate, comprising: laminating the resin layer (I), which is formed by using a composition containing the compound C having:

(In the formula (1), X ₁ represents an aromatic ring or an alicyclic structure, and n1 and n2 each independently represent an integer of 0 to 3.)

(In the formula (2), R ₁ represents a hydrogen atom, a hydrocarbon group having 1 to 3 carbon atoms or a carbonyl group, and m 1 to m 3 each independently represent an integer of 0 to 3.) A gas barrier material containing the laminate according to claim 1. A packaging material containing the laminate according to claim 1.

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