JP2018094885A - Gas barrier laminated sheet, packaging material, and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated sheet including a layer excellent in flexibility and heat and moisture resistance, and to provide a packaging material and a molded article using the laminated sheet.SOLUTION: A laminated sheet 10 includes a substrate 1, an inorganic compound layer 3 formed on the substrate 1, and a layer 5 provided on the inorganic compound layer 3 and formed of a composition containing a polymer compound (A) having a hydroxyl group, at least one compound (B) selected from the group consisting of organotitanium compounds and organozirconium compounds, and a silicon compound (C).SELECTED DRAWING: Figure 1

Description

  The present invention relates to a laminated sheet, a packaging material, and a molded product.

  In recent years, packaging materials used for the packaging of food and non-food products such as pharmaceuticals and electronic components have been designed to prevent the permeation of gases such as oxygen and water vapor in order to suppress the alteration of the contents and maintain the functions and properties of the contents. It is required to have a gas barrier property for blocking the above.

As a gas barrier sheet used for packaging foods and non-foods, an inorganic vapor deposition film in which an inorganic vapor deposition layer is provided on at least one surface of a substrate such as a polyester film is widely used (for example, Patent Document 1).
However, when an inorganic vapor deposition film as proposed in Patent Document 1 is stressed by bending, stretching, or the like, the inorganic vapor deposition layer is damaged, and the gas barrier property tends to be lowered.

In Patent Document 2, an aqueous solution or a water / alcohol mixed solution containing a water-soluble polymer and at least one of at least one alkoxide, a hydrolyzate of the alkoxide, and tin chloride is formed on the inorganic vapor deposition layer. There has been proposed a gas barrier laminated film provided with a gas barrier film formed by applying a coating agent as a main agent and drying by heating.
This gas barrier laminate film exhibits high gas barrier properties, and retains a certain degree of gas barrier properties even after bending, stretching, etc., by coating the inorganic vapor deposition layer with a flexible gas barrier coating. It is also said to have heat resistance, moisture resistance and water resistance.

  However, the heat and humidity resistance of the gas barrier laminate film of Patent Document 2 is not sufficient, and when exposed to a high temperature and high humidity atmosphere, for example, when used as a packaging material that requires hot water treatment such as boil treatment and retort treatment, The gas barrier coating swells and the gas barrier properties deteriorate. Further, the gas barrier laminated film of Patent Document 2 does not have sufficient gas barrier properties after processing such as bending and stretching, and depending on the type and degree of processing of the laminated film, damage due to processing reaches the inorganic vapor deposition layer. Gas barrier properties are impaired.

JP-A-9-123338 Japanese Patent No. 2790054

  This invention is made | formed in view of the said situation, Comprising: It aims at provision of the laminated sheet provided with the layer excellent in the softness | flexibility and heat-and-moisture resistance, a packaging material using this, and a molded article.

The present invention has the following aspects.
<1> The laminated sheet according to the first aspect of the present invention is provided on a base material, an inorganic compound layer formed on the base material, and the inorganic compound layer, and a polymer compound having a hydroxyl group ( A), at least one compound (B) selected from the group consisting of an organic titanium compound and an organic zirconium compound, and a layer formed from a composition containing a silicon compound (C).
<2> The compound (B) may contain at least one compound (B1) selected from the group consisting of a metal chelate compound, a hydrolyzate of the metal chelate compound, and a condensate of the metal chelate compound. .
<3> The silicon compound (C) may include at least one compound (C1) selected from the group consisting of a compound represented by the following formula (c1) and a hydrolyzate thereof.
Si (OR ¹ ) ₄ (c1)
(In the formula, R ¹ is an alkyl group having 1 to 4 carbon atoms or an alkoxyalkyl group having 1 to 4 carbon atoms, and four R ¹ in the formula may be the same or different.)
<4> The mass ratio between the polymer compound (A) and the sum of the compound (B) and the compound (C1) in terms of SiO ₂ may be in the range of 25/75 to 30/70. .
<5> The ratio of the compound (B) to the sum of the polymer compound (A), the compound (B), and the amount of the compound (C1) in terms of SiO ₂ is 3 to 8% by mass. Also good.
<6> The inorganic compound layer may be a gas barrier layer made of an inorganic material.
<7> The packaging material according to the second aspect of the present invention includes the laminated sheet according to the above aspect.
<8> The packaging material according to the above aspect may be a packaging material for hot water treatment.
<9> The molded product according to the third aspect of the present invention includes the packaging material according to the above aspect.
<10> The molded product according to the above aspect may be a vertical bag-filling sealing bag, a vacuum packaging bag, a pouch with a spout, a laminate tube container, an infusion bag, a container lid, a paper container, or a vacuum insulator.

  According to the aspect of the present invention, it is possible to provide a laminated sheet having a layer excellent in flexibility and heat and humidity resistance, a packaging material using the laminated sheet, and a molded product.

It is sectional drawing which shows typically the lamination sheet which concerns on one Embodiment of this invention. It is sectional drawing which shows typically the example which provided the anchor coat layer in the lamination sheet which concerns on one Embodiment of this invention.

  Hereinafter, the present invention will be described in detail according to preferred embodiments.

<First embodiment>
FIG. 1 is a cross-sectional view schematically showing a laminated sheet 10 according to the first embodiment of the present invention.
The laminated sheet 10 according to the first embodiment of the present invention is provided on the substrate 1, the inorganic compound layer 3 formed on the substrate 1, the inorganic compound layer 3, and a polymer compound having a hydroxyl group ( A), a layer 5 formed of a composition containing at least one compound (B) selected from the group consisting of an organic titanium compound and an organic zirconium compound, and a silicon compound (C).

<Base material>
Examples of the material of the substrate 1 include single-layer or multilayer substrates of plastics, papers, and rubbers. Among these materials of the base material 1, it is preferable that plastics is the outermost layer from the viewpoint of adhesion between the base material and the inorganic compound layer (gas barrier layer).

  Examples of plastics include polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyolefin films such as polyethylene and polypropylene, polystyrene films, polyamide films such as 66-nylon, polycarbonate films, polyacrylonitrile films, and polyimide films. Engineering plastic film and the like. One kind of these resin materials may be used alone, or a material obtained by blending two or more kinds into a film shape may be used as a substrate.

As the plastic film, either a stretched film or an unstretched film may be used, and a film having mechanical strength and dimensional stability is preferable. In particular, a film arbitrarily stretched in the biaxial direction is preferably used.
When the laminated sheet is used as a packaging material, a polyamide film and a polyester film are preferable, and a polyester film is more preferable in consideration of price, moisture resistance, filling suitability, texture, and discardability.
Surface activation treatment such as corona treatment, flame treatment, and plasma treatment may be applied to the surface of the substrate 1 from the viewpoint of adhesion between the substrate 1 and the layer to be adhered.

  The thickness of the base material 1 can be appropriately set according to the use of the laminated sheet. For example, when a laminated sheet is used as a packaging material, the thickness of the base material 1 is not particularly limited, but in view of suitability as a packaging material and workability, it is preferably 3 to 200 μm for practical use. 6 to 30 μm is more preferable.

<Inorganic compound layer>
The inorganic compound layer 3 is composed of an inorganic material.
As the inorganic material constituting the inorganic compound layer 3, an inorganic material capable of constituting a layer (gas barrier layer) for imparting gas barrier properties such as oxygen barrier property and water vapor barrier property to the laminated sheet is appropriately selected. Examples thereof include inorganic oxides such as aluminum (metal aluminum), aluminum oxide, silicon oxide, magnesium oxide, and tin oxide.
As the inorganic compound layer 3, an inorganic vapor deposition layer etc. are mentioned, for example.
As an inorganic vapor deposition layer, the vapor deposition film (inorganic vapor deposition film) which vapor-deposited the inorganic material on the base material 1 by the vapor deposition method is preferable.
Hereinafter, the inorganic compound layer 3 may be referred to as an inorganic vapor deposition layer or a gas barrier layer.

The aluminum oxide preferably has an abundance ratio of aluminum (Al) to oxygen (O) of Al: O = 1: 1.5 to 1: 2.0. For example, an aluminum oxide vapor deposition film is formed by reactive vapor deposition, reactive sputtering, or reactive ion in which a thin film is formed in an atmosphere of a mixed gas of oxygen gas and inert gas such as carbon dioxide gas using aluminum as an evaporation material. It can be formed by plating. At this time, if aluminum is reacted with oxygen, it should be Al: O = 1: 1.5 since it is stoichiometrically Al ₂ O ₃ . However, depending on the vapor deposition method, some of the chemical species in which aluminum is present as it is or chemical species in which aluminum peroxide is present may be included in the deposited film. In this case, when the abundance ratio of the elements in the deposited film is measured using an X-ray photoelectron spectrometer (XPS) or the like, it can be seen that Al: O = 1: 1.5 cannot be said. In general, a chemical species with less oxygen than Al: O = 1: 1.5 and a large amount of aluminum can provide a good gas barrier property to form a dense film, but the deposited film is colored black and has a light transmission amount. Tend to be lower. Conversely, chemical species with more oxygen and lower aluminum content than Al: O = 1: 1.5 form a sparse film (film with low density), and a transparent film with high light transmission but poor gas barrier properties. can get.
Silicon oxide is particularly preferred when water resistance is required.

  The thickness of the inorganic compound layer 3 varies depending on the use of the laminated sheet 10 and the film thickness of the layer 5 described later, but is preferably 5 to 300 nm, and more preferably 10 to 50 nm. If the thickness of the inorganic compound layer 3 is less than the lower limit (5 nm) of the above range, the continuity of the inorganic compound layer 3 may be impaired. When the thickness of the inorganic compound layer 3 is larger than the upper limit (300 nm) of the above range, the flexibility of the inorganic compound layer 3 is lowered, and there is a possibility that cracking may occur due to external factors such as bending and pulling after film formation.

<Anchor coat layer>
FIG. 2 is a cross-sectional view schematically showing a laminated sheet 20 including the anchor coat layer 2 in the first embodiment of the present invention.
In order to increase the adhesion of the inorganic compound layer 3 to the substrate 1, the inorganic compound layer 3 may be formed on the substrate 1 via the anchor coat layer 2. Examples of the material constituting the anchor coat layer 2 include urethane resins, epoxy resins, acrylic resins, and polyester resins. In addition, other additives such as a curing agent and a silane coupling agent may be added to these resins depending on applications. In particular, a combination of an acrylic polyol, an isocyanate compound, and a silane coupling agent is preferable. When the anchor coat layer 2 composed of a combination of an acrylic polyol, an isocyanate compound, and a silane coupling agent is used, stable high adhesion is obtained between the substrate 1 and the vapor deposition layer (inorganic compound layer) 3. be able to.

  The thickness of the anchor coat layer 2 is not particularly limited as long as the thickness on the surface of the substrate 1 is uniform, but is preferably 0.01 to 2 μm, more preferably 0.05 to 0.5 μm. preferable. If the thickness of the anchor coat layer 2 is not less than the lower limit (0.01 μm) of the above range, the uniformity of the thickness of the anchor coat layer 2 is high, and the adhesion of the inorganic vapor deposition layer to the substrate 1 is more excellent. If the thickness of the anchor coat layer 2 is equal to or less than the upper limit (2 μm) of the above range, the anchor coat layer 2 maintains sufficient flexibility, and cracks due to external factors are unlikely to occur.

(Layer formed from composition (I))
It is formed from a composition (I) comprising a polymer compound (A) having a hydroxyl group, at least one compound (B) selected from the group consisting of an organic titanium compound and an organic zirconium compound, and a silicon compound (C). Layer (composition (I) layer) 5.

"Polymer compound having hydroxyl group (A)"
The polymer compound (A) is not particularly limited as long as it is a polymer compound having a hydroxyl group.
The polymer compound (A) is preferably a vinyl alcohol polymer from the viewpoint of gas barrier properties. A vinyl alcohol polymer is a polymer containing vinyl alcohol units. Examples of the vinyl alcohol polymer include polyvinyl alcohol (hereinafter also referred to as “PVA”), an ethylene-vinyl alcohol copolymer, a modified vinyl alcohol polymer, and the like.
The degree of polymerization of the vinyl alcohol polymer is preferably 500 or more and 3000 or less, and more preferably 1000 or more and 3000 or less.

Among vinyl alcohol polymers, PVA is particularly preferable. When the polymer compound (A) is PVA, the gas barrier property is most excellent.
Here, PVA is a compound generally obtained by saponifying polyvinyl acetate. The PVA may be completely saponified PVA in which only a few percent of acetic acid groups remain, or may be partially saponified PVA in which the remaining amount of acetic acid groups is larger than that of completely saponified PVA. The use of PVA having a high degree of saponification is preferred because of its high water resistance, and fully saponified PVA is particularly preferred.
There are various degrees of polymerization of PVA from 300 to several thousand, and PVA having any degree of polymerization may be used, but PVA having a high degree of polymerization is preferable because of high water resistance. The polymerization degree of PVA is preferably 500 or more and 3000 or less, and more preferably 1000 or more and 3000 or less.

“At least one compound (B) selected from the group consisting of organic titanium compounds and organic zirconium compounds”
The compound (B) is at least one compound selected from the group consisting of an organic titanium compound and an organic zirconium compound.
Further, the compound (B) may contain at least one compound (B1) selected from the group consisting of metal chelate compounds, hydrolysates of metal chelate compounds, and condensates of metal chelate compounds.
In other words, the compound (B) is a group of titanium chelate compound, hydrolyzate of titanium chelate compound, condensate of titanium chelate compound, zirconium chelate compound, hydrolyzate of zirconium chelate compound, and condensate of zirconium chelate compound. It may contain at least one compound (B1) selected from:

Examples of the organic titanium compound include titanium diisopropoxybis (ethyl acetoacetate), titanium dioctyloxybis (octylene glycolate), titanium tetraacetylacetonate and titanium diisopropoxybis (acetylacetonate), Examples include titanium chelates such as isopropoxybis (triethanolaminate), and titanium alkoxides such as titanium tetra-2-ethylhexoxide, titanium butoxy dimer, titanium tetranormal butoxide and titanium tetraisopropoxide, and compounds It can be appropriately selected and used in consideration of its own stability, crosslinking rate, crosslinking curing rate, and the like.
Further, the organic titanium compound may contain at least one of the hydrolyzate and condensate of the titanium chelate, and contains at least one of the hydrolyzate and condensate of the titanium alkoxide. Also good.

Examples of the organic zirconium compound include zirconium such as zirconium tetraacetonate, zirconium dibutoxybis (ethyl acetate), zirconium monobutoxyacetylacetonate bis (ethyl acetate), zirconium tributoxymonoacetylacetonate, and zirconium tetraacetylacetonate. Chelates and zirconium alkoxides such as zirconium tetranormal butoxide and zirconium tetranormal propoxide can be mentioned, and can be appropriately selected and used in consideration of the stability of the compound itself, the crosslinking rate and the crosslinking effect rate.
The organic zirconium compound may contain at least one of the hydrolyzate and condensate of the zirconium chelate, and contains at least one of the hydrolyzate and condensate of the zirconium alkoxide. Also good.

"Silicon compound (C)"
Examples of the silicon compound (C) include a compound represented by the following formula (c1) (hereinafter also simply referred to as “Si (OR ¹ ) ₄ ”) and a hydrolyzate thereof (represented by the formula (c1)). And at least one compound (C1) selected from the group consisting of compound hydrolysates.
Si (OR ¹ ) ₄ (c1)
(In the formula, R ¹ is an alkyl group having 1 to 4 carbon atoms or an alkoxyalkyl group having 1 to 4 carbon atoms, and four R ¹ in the formula may be the same or different.)

In Si (OR ¹ ) ₄ , R ¹ is preferably CH ₃ , C ₂ H ₅ , or C ₂ H ₄ OCH ₃ . Si ^(OR ₁₎ can be used singly or in combination of two or more as _4.
The hydrolyzate of Si (OR ¹ ) ₄ can be obtained by a known method. Typically, Si (OR ¹ ) ₄ is hydrolyzed using an acid or alkali catalyst, alcohol and water. In view of easy control of hydrolysis, it is preferable to use an acid catalyst. At this time, in order to further control the hydrolysis, a generally known catalyst may be added.

The composition (I) is at least one compound (B) selected from the group consisting of a polymer compound (A), an organic titanium compound, and an organic zirconium compound as long as it does not impair gas barrier properties and heat and humidity resistance. ) And other components other than the silicon compound (C) may be further included.
Examples of other components include additives such as plasticizers, resins, dispersants, surfactants, softeners, stabilizers, antiblocking agents, film forming agents, pressure-sensitive adhesives, oxygen absorbers, and viscosity minerals. .

In the composition (I), the content of the polymer compound (A) is at least one compound (B) selected from the group consisting of the polymer compound (A), an organic titanium compound and an organic zirconium compound, and a compound. the total of SiO ₂ in terms of (C1), preferably from 20 to 35 wt%, more preferably 25 to 30 wt%. When the content of the polymer compound (A) is not less than the lower limit (20% by mass) of the above range, the abuse resistance (deterioration resistance) is more excellent, and is not more than the upper limit (35% by mass) of the above range. And better heat and humidity resistance.
The SiO ₂ equivalent amount of the compound (C1), is the amount at which the compound (C1) is assumed that all became SiO ₂ (the amount on the assumption that all of the SiO _2).
The abuse resistance means resistance to physical loads such as bending, stretching, compression, and shearing. Abuse in the specification of the present application means that the physical load is applied to an object (for example, a laminated sheet, a laminated sheet test sample, or the like).

The content of at least one compound (B) selected from the group consisting of an organic titanium compound and an organic zirconium compound is at least one selected from the group consisting of the polymer compound (A), an organic titanium compound and an organic zirconium compound. the compound (B), the total of SiO ₂ in terms of the compound (C1), preferably from 3 to 8% by weight, more preferably 3-6 wt%. From the organotitanium compound and the organozirconium compound with respect to the total of at least one compound (B) selected from the group consisting of the polymer compound (A), the organotitanium compound, and the organozirconium compound and the amount of the compound (C1) in terms of SiO ₂ Severe treatment such as boil treatment and retort sterilization treatment without impairing abuse resistance when the ratio of at least one compound (B) selected from the group consisting of is within the above range (3 to 8% by mass) It is easy to obtain a gas barrier property with high heat and humidity resistance that does not deteriorate. When the proportion of at least one compound (B) selected from the group consisting of an organic titanium compound and an organic zirconium compound is less than the lower limit (3% by mass) of the above range, the crosslinking reaction is insufficient and the heat and humidity resistance is insufficient. There is a risk of becoming. When it is larger than the upper limit (8% by mass) of the above range, the crosslinking reaction is excessive, the abuse resistance is impaired, or at least one compound (B) selected from the group consisting of an organic titanium compound and an organic zirconium compound is used. There is a possibility that unreacted components remain and become pores, resulting in a decrease in gas barrier properties.

In the composition (I), the total amount of the polymer compound (A), the at least one compound (B) selected from the group consisting of an organotitanium compound and an organozirconium compound, and a compound (C1) in terms of SiO ₂ The mass ratio ((A) / [(B) + (C1)]) is preferably in the range of 20/80 to 35/65, more preferably 25/75 to 30/70.
If (A) / [(B) + (C1)] is within the above range (20/80 to 35/65), the heat and humidity resistance and high gas barrier properties necessary for hot water treatment such as boil treatment and retort treatment are obtained. Not only can it be obtained, but the abuse resistance due to the coating flexibility when considered as a packaging material is sufficiently imparted.
On the other hand, when (A) / [(B) + (C1)] is larger than the upper limit (35/65), the heat and humidity resistance may be insufficient. When (A) / [(B) + (C1)] is smaller than the lower limit (20/80), the gas barrier property becomes insufficient, the flexibility becomes low, and the abuse resistance becomes insufficient. There is a risk.
In addition, when (A) / [(B) + (C1)] is in the range of 25/75 to 30/70, particularly excellent heat and humidity resistance and high gas barrier properties can be obtained. It also has excellent abuse resistance due to its coating flexibility.

In the composition (I), the total amount of the polymer compound (A), at least one compound (B) selected from the group consisting of an organic titanium compound and an organic zirconium compound and the SiO ₂ equivalent amount of the compound (C1) is The total solid content is preferably 70% by mass or more, and more preferably 90% by mass or more. The upper limit of the content (total amount) is not particularly limited, and may be 100% by mass.

  The composition (I) layer 5 includes, for example, a polymer compound (A), at least one compound (B) selected from the group consisting of an organic titanium compound and an organic zirconium compound, and a silicon compound on the substrate 1. (C) and the coating liquid containing a solvent are applied, the coating film comprised from the said coating agent is formed, and it can form by drying the said coating film.

<Method for producing laminated sheet>
The laminated sheet 10 according to the present embodiment can be manufactured by, for example, a manufacturing method including the following steps (α1) and (α2).
(Α1): A step of forming an inorganic compound layer (inorganic vapor deposition layer) 3 on one surface of the substrate 1.
(Α2): At least one compound (B) selected from the group consisting of a polymer compound (A) and an organic titanium compound and an organic zirconium compound on the surface of the substrate 1 on which the inorganic vapor deposition layer 3 is formed. Applying a coating liquid (a) containing a silicon compound (C) and a solvent, followed by drying to form the composition (I) layer 5.

[Step (α1)]
There are various methods for forming the inorganic compound layer (inorganic vapor deposition layer) 3 composed of an inorganic material. For example, a known vapor deposition method can be used. Examples of the vapor deposition method include a vacuum vapor deposition method, a sputtering method, an ion plating method, a chemical vapor deposition method, and the like.
As the heating means (heating method) of the vacuum evaporation apparatus by the vacuum evaporation method, an electron beam heating method, a resistance heating method, an induction heating method, or the like is preferable. In order to improve the adhesion of the inorganic vapor deposition layer 3 to the substrate 1 and the denseness of the vapor deposition film (inorganic vapor deposition layer), it is also possible to use a plasma assist method or an ion beam assist method. Further, in order to increase the transparency of the deposited film, reactive deposition such as blowing oxygen gas may be performed during the deposition.

[Step (α2)]
The coating liquid (a) is the same as the composition (I) except that it contains a solvent.
As the solvent of the coating liquid (a), water or a mixed solvent of water and an organic solvent is preferable, and a mixed solvent of water and a lower alcohol having 1 to 5 carbon atoms is more preferable.

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

  The method for drying the coating film is not particularly limited, and examples thereof include a hot air drying method, a hot roll contact method, an infrared heating method, and a microwave heating method. Drying may be performed by any one of or a combination of hot air drying method, hot roll contact method, infrared heating method, microwave heating method and the like. Although there is no limitation in particular as drying temperature, When using the water mentioned above as a solvent, or the mixed solvent of water and an organic solvent, 50-160 degreeC is preferable normally. In addition, the pressure during drying is usually preferably normal pressure or reduced pressure, and is preferably normal pressure from the viewpoint of facility simplicity.

  In addition, when laminating two or more composition (I) layers (for example, laminating composition (I) layers on both surfaces of a base material), coating of coating liquid (a) for forming each layer And drying may be performed continuously, and may be performed discontinuously through a winding process and a curing process.

  Although the laminated sheet according to the first embodiment of the present invention has been described above, the present invention is not limited to these embodiments. Each configuration in the above embodiment, a combination thereof, and the like are examples, and the addition, omission, replacement, and other modifications of the configuration can be made without departing from the spirit of the present invention.

The laminated sheet according to the present embodiment may not have an inorganic vapor deposition layer. In view of gas barrier properties, particularly water vapor barrier properties, and usefulness of providing the composition (I) layer, it is preferable to have an inorganic vapor deposition layer.
In the said embodiment, although the example in which the inorganic vapor deposition layer 3 and the composition (I) layer 5 were laminated | stacked in this order on one side of the base material 1 was shown, arrangement | positioning of each layer is not limited to this. For example, the inorganic vapor deposition layer and the composition (I) layer 5 may be provided on both surfaces of the substrate, respectively, the inorganic vapor deposition layer is provided on one surface (first surface) of the substrate, and the other surface (second surface). The composition (I) layer may be provided on the surface. In terms of abuse resistance, it is preferable to provide an inorganic vapor deposition layer between the base material and the composition (I) layer.
Moreover, the composition (I) layer may be laminated | stacked through arbitrary other layers between the composition (I) layer and the inorganic vapor deposition layer. Furthermore, another layer may be laminated on the composition (I) layer.

In the laminated sheet according to the present embodiment, strength is imparted to the laminated sheet, sealing properties and easy-openability at the time of sealing are imparted to the laminated sheet, design properties are imparted to the laminated sheet, and light blocking properties are provided. For the purpose of imparting to the laminated sheet, another base material may be further laminated on the composition (I) layer.
The other substrate is appropriately selected according to the purpose and is not particularly limited, but usually plastic films and papers are preferable. Such a plastic film or paper may be a single substrate used alone, or two or more substrates may be laminated. For example, a plastic film and paper may be laminated and used as another substrate.

The laminated sheet according to the present embodiment is used for molded products such as a vertical bag-filling sealing bag, a vacuum packaging bag, a pouch with a spout, a laminated tube container, an infusion bag, a container lid, a paper container, and a vacuum heat insulator, which will be described later. In the case where the laminated sheet is used, it is preferable that a heat-sealable layer is disposed as the other base material on one or both outermost layers. Thereby, a lamination sheet becomes what has heat-sealing property, and the process to a molded article becomes easy.
A polyolefin layer is preferred as the heat-sealable layer. The polyolefin is not particularly limited as long as it is suitable for heat sealing, and examples thereof include low density polyethylene (LDPE) and unstretched polypropylene (CPP).
The thickness of the heat-sealable layer is not particularly limited, but can be appropriately set within a range of, for example, 5 to 300 μm, preferably within a range of 10 to 100 μm.

As a method for laminating other base materials, a method of laminating by an laminating method using an adhesive may be mentioned. Specific examples of the laminating method include a dry laminating method, a wet laminating method, and an extrusion laminating method.
The laminated sheet according to the present embodiment has a printed layer and a vapor-deposited layer for the purpose of imparting design properties to the laminated sheet, imparting light blocking properties to the laminated sheet, imparting moisture resistance to the laminated sheet, and the like. It may be provided.

(Use)
As a use of the laminated sheet according to the present embodiment, a packaging material is preferable. The laminated sheet according to the present embodiment has a high gas barrier property even under high temperature and high humidity, and can maintain the gas barrier property at a high level even after hot water treatment such as boil treatment and retort treatment. In addition, gas barrier properties are unlikely to deteriorate even after abuse such as bending or stretching. For this reason, it is possible to provide post-processing such as printing process, dry lamination, melt-extrusion lamination, thermocompression lamination using this, and provide a packaging material with a wide range of practical use used in the packaging field of foods, pharmaceuticals, etc. .
However, the use of the laminated sheet according to the present embodiment is not limited to this, and can be used for uses other than packaging materials.
Applications other than packaging materials include, for example, LCD substrate films, organic EL substrate films, electronic paper substrate films, electronic device sealing films, PDP films, LED films, IC tag films, solar cell bags Sheets, films related to electronic devices such as protective films for solar cells, optical communication members, flexible films for electronic devices, diaphragms for fuel cells, sealing films for fuel cells, substrate films for various functional films, and the like.

<Second embodiment>
≪Packaging materials≫
The packaging material according to the second embodiment of the present invention includes the laminated sheet according to the first embodiment of the present invention described above.
The packaging material according to the present embodiment may be composed of the laminated sheet according to the first embodiment of the present invention, and includes the laminated sheet according to the first embodiment and other materials. Also good. Examples of other materials include a thermoplastic resin film and paper.

The use to which the packaging material according to this embodiment is applied is not particularly limited, and can be used as a packaging material for various articles.
When the laminated sheet according to the first embodiment of the present invention has gas barrier properties, the packaging material according to the second embodiment of the present invention is preferably used as a packaging material for articles that are likely to deteriorate due to the influence of oxygen, water vapor, etc. Among these, it is preferably used as a food packaging material. In addition to food packaging materials, they can be preferably used as packaging materials for non-food products, for example, chemicals such as agricultural chemicals and pharmaceuticals, medical tools, machine parts, precision materials, and the like.

The laminated sheet according to the first embodiment of the present invention is excellent in heat and humidity resistance, and, for example, when the laminated sheet is subjected to hot water treatment such as boil treatment and retort treatment, gas barrier properties and interlayer adhesion are unlikely to deteriorate. Therefore, the packaging material according to the second embodiment of the present invention is useful as a packaging material for hot water treatment.
Examples of the hot water treatment include boil treatment and retort treatment.

The boil treatment is a method of sterilizing with wet heat to preserve foods and the like. Although it depends on the contents, the boil treatment includes a method of sterilizing a packaging material in which food or the like is packaged at 60 to 100 ° C. and atmospheric pressure for 10 to 120 minutes.
There are two types of boil treatments: a batch method in which a hot water bath is used and immersed in a hot water bath at a constant temperature and taken out after a predetermined time, and a continuous method in which the hot water bath is sterilized through a tunnel type.

In general, retort treatment is a method of sterilizing microorganisms such as molds, yeasts, and bacteria in order to preserve foods and the like. Examples of the retort treatment include a method in which a packaging material in which food is packaged is subjected to pressure sterilization treatment at 105 to 140 ° C. and 0.15 to 0.3 MPa for 10 to 120 minutes.
The retort apparatus used for the retort treatment includes a steam type using heated steam, a hot water type using pressurized superheated water, and the like, which are properly used depending on the sterilization conditions of food or the like as the contents.

  The contents packed with the hot water treatment packaging material are not particularly limited, and may be food or non-food. Examples of the food include curry, cooking seasoning sauce, and processed meat products. Examples of non-food include medical products such as infusion preparations, and industrial products such as semiconductors and precision materials.

<Third embodiment>
≪Molded body≫
The molded product according to the third embodiment of the present invention includes the packaging material according to the second embodiment of the present invention described above.
Examples of the molded product according to the present embodiment include a container, a member constituting a part of the container, and the like. Specific examples include a vertical bag-filling sealing bag, a vacuum packaging bag, a pouch with a spout, and a laminated tube container. , Infusion bags, container lids, paper containers, vacuum insulators and the like.
The molded product according to this embodiment can be manufactured by a known method. For example, in the manufacture of vertical bag filling and sealing bags, vacuum packaging bags, spout pouches, laminated tube containers, infusion bags, container lids, paper containers, vacuum insulators, etc., heat sealing of packaging materials is usually performed. . Therefore, as the packaging material constituting the above-described molded products, packaging materials in which a heat-sealable layer is disposed on one or both outermost layers are usually preferable.

  Hereinafter, the present invention will be specifically described based on Examples and Comparative Examples. However, the present invention is not limited to the following examples.

(Preparation Example 1)
PVA solution with a polymerization degree of 2400 (manufactured by Kuraray, PVA124, completely saponified PVA) is diluted with a mixed solvent of water / methyl alcohol = 90/10 (mass ratio) so that the solid content concentration becomes 5% by mass, and the PVA solution Adjusted.
An organic zirconium compound (manufactured by Matsumoto Fine Chemical, ZC-126, an aqueous solution of zirconyl chloride compound) is added to the PVA solution so as to obtain the desired solid content ratio, and the mixture is stirred for 1 hour, and an organic zirconium compound having a solid content of 5.5% by mass A compound-added PVA solution was prepared.
Next, 0.1N hydrochloric acid is added to tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ , hereinafter referred to as “TEOS”), and the mixture is stirred for 30 minutes to be hydrolyzed to a solid content of 3% by mass (in terms of SiO ₂ ). A hydrolysis solution of was prepared.
The organic zirconium compound-added PVA solution and the TEOS hydrolysis solution are mixed so that the PVA / organozirconium compound / TEOS (in terms of SiO ₂ ) is 25/5/70 in terms of the solid mass ratio, and the coating liquid (a1) is mixed. Prepared.

(Preparation Example 2)
A coating solution (a2) was prepared in the same manner as in Preparation Example 1, except that PVA / organozirconium compound / TEOS (SiO ₂ equivalent) was 27/8/65.

(Preparation Example 3)
A coating liquid (a3) was prepared in the same manner as in Preparation Example 1, except that PVA / organozirconium compound / TEOS (SiO ₂ equivalent) was changed to 30/4/66.

(Preparation Example 4)
A coating solution (a4) was prepared in the same manner as in Preparation Example 1, except that PVA / organozirconium compound / TEOS (SiO ₂ equivalent) was changed to 30/6/64.

(Preparation Example 5)
Coating liquid (a5) in the same manner as in Preparation Example 4 except that the organic zirconium compound was changed to an organic titanium compound (manufactured by Matsumoto Fine Chemical, TC-400, 2-propanol solution of titanium diisopropoxybis (triethanolaminate)) Was prepared.

(Preparation Example 6)
Coating liquid as in Preparation Example 4 except that half of the organozirconium compound was changed to an organotitanium compound, and PVA / organozirconium compound / organotitanium compound / TEOS (SiO ₂ equivalent) was changed to 30/3/3/64. (A6) was prepared.

(Preparation Example 7)
A coating solution (b1) was prepared in the same manner as in Preparation Example 1, except that PVA / organozirconium compound / TEOS (SiO ₂ equivalent) was changed to 27/2/71.

(Preparation Example 8)
A coating liquid (b2) was prepared in the same manner as in Preparation Example 1, except that PVA / organozirconium compound / TEOS (SiO ₂ equivalent) was changed to 27/9/64.

(Preparation Example 9)
A coating solution (b3) was prepared in the same manner as in Preparation Example 1 except that PVA / organozirconium compound / TEOS (SiO ₂ equivalent) was 40/3/57.

(Preparation Example 10)
A coating solution (b4) was prepared in the same manner as in Preparation Example 1, except that PVA / organozirconium compound / TEOS (SiO ₂ equivalent) was 40/8/52.

(Preparation Example 11)
The PVA solution and the TEOS hydrolyzed solution were mixed so that the PVA / TEOS (in terms of SiO ₂ ) was 27/73 in terms of the solid mass ratio, and the same as in Preparation Example 1 except that the organic zirconium compound was not added. A coating liquid (b5) was prepared.

Example 1
On a biaxially stretched polyethylene terephthalate film (PET: manufactured by Toray, Lumirror (registered trademark) P60, thickness 12 μm, inner corona treatment), metal aluminum is evaporated by an electron beam heating vacuum deposition apparatus, and oxygen gas is present there. Then, aluminum oxide was deposited to form a deposited film (gas barrier layer, inorganic compound layer, inorganic deposited layer) having a thickness of 20 nm.

  Next, the coating liquid (a1) is applied onto the gas barrier layer with a bar coater and dried at 120 ° C. for 1 minute with a dryer to form a film (layer (a1)) having a film thickness of about 0.5 μm. A laminated sheet having the configuration of [PET / gas barrier layer / layer (a1)] was obtained.

(Example 2)
[PET / gas barrier layer / layer (a2)] was carried out in the same manner as in Example 1 except that the coating liquid (a2) was used instead of the coating liquid (a1) to form a film (layer (a2)). A laminated sheet having the following structure was obtained.

(Example 3)
[PET / gas barrier layer / layer (a3)] except that the coating liquid (a3) was used instead of the coating liquid (a1) to form a film (layer (a3)). A laminated sheet having the following structure was obtained.

Example 4
[PET / gas barrier layer / layer (a4)] was performed in the same manner as in Example 1 except that the coating liquid (a4) was used instead of the coating liquid (a1) to form a film (layer (a4)). A laminated sheet having the following structure was obtained.

(Example 5)
[PET / gas barrier layer / layer (a5)] was carried out in the same manner as in Example 1 except that the coating liquid (a5) was used instead of the coating liquid (a1) to form a film (layer (a5)). A laminated sheet having the following structure was obtained.

(Example 6)
[PET / gas barrier layer / layer (a6)] except that the coating liquid (a6) was used instead of the coating liquid (a1) to form a film (layer (a6)). A laminated sheet having the following structure was obtained.

(Comparative Example 1)
On the biaxially stretched polyethylene terephthalate film (PET: manufactured by Toray, Lumirror P60, thickness 12 μm, inner corona treatment), the metal aluminum is evaporated by a vacuum vapor deposition device using an electron beam heating method, oxygen gas is introduced therein, Aluminum oxide was deposited to form a deposited film (gas barrier layer, inorganic compound layer, inorganic deposited layer) having a thickness of 20 nm.

  Next, the coating liquid (b1) is applied onto the gas barrier layer with a bar coater, and dried at 120 ° C. for 1 minute with a dryer to form a film (layer (b1)) having a film thickness of about 0.5 μm. A laminated sheet having the configuration of [PET / gas barrier layer / layer (b1)] was obtained.

(Comparative Example 2)
A laminated sheet was obtained by performing the same operation as in Comparative Example 1 except that the coating liquid (b2) was used instead of the coating liquid (b1) to form a film (layer (b2)).

(Comparative Example 3)
A laminated sheet was obtained by performing the same operation as in Comparative Example 1 except that the coating liquid (b3) was used instead of the coating liquid (b1) to form a film (layer (b3)).

(Comparative Example 4)
A laminated sheet was obtained by performing the same operation as in Comparative Example 1 except that the coating liquid (b4) was used instead of the coating liquid (b1) to form a film (layer (b4)).

(Comparative Example 5)
A laminated sheet was obtained by performing the same operation as in Comparative Example 1 except that the coating liquid (b5) was used instead of the coating liquid (b1) to form a film (layer (b5)).

[1. Preparation of laminate film]
Using the laminated sheets obtained in Examples 1 to 6 and Comparative Examples 1 to 5, laminate sheets were produced by the following procedure.
Ny (stretched nylon film) and CPP (polypropylene film) were sequentially bonded to the laminated surface of the laminated sheet using a multi coater MC350 manufactured by HIRANO TECSEED, using an adhesive. Thereafter, the film was cured at 40 ° C. for 3 days to obtain a laminate sheet having a structure of [Laminated sheet / Adhesive / Ny / Adhesive / CPP].
Furthermore, LLDPE (linear low density polyethylene) was bonded to the laminated surface of the laminated sheet to obtain a laminated sheet having a configuration of [Laminated sheet / Adhesive / LLDPE].
The laminated surface is a surface on which a gas barrier layer and a film are laminated.

As the adhesive, a two-component curable adhesive, Takelac A525 (main agent) / Takenate A52 (hardener) manufactured by Mitsui Chemicals, Inc. was used.
As Ny, a stretched nylon film, Emblem ONMB (15 μm) manufactured by Unitika Ltd. was used.
As the CPP, a polypropylene film manufactured by Toray Film Processing Co., Ltd., Treffan ZK93FM (60 μm) was used.
As LLDPE, a linear low-density polyethylene film, TUX-TCS (60 μm) manufactured by Mitsui Chemicals, Inc. Toro Cello Co., Ltd. was used.

  The following evaluation was performed about the obtained laminate sheet. The results are shown in Table 1.

[2. Evaluation of gas barrier properties (before abuse)]
With respect to the laminate film (configuration: laminated sheet / adhesive / LLDPE), oxygen permeability and water vapor permeability were measured by the following procedure. The results are shown in Table 1 as oxygen permeability and water vapor permeability of “base paper”. “Base paper” means the laminate film before the abuse.

(Measurement of oxygen permeability)
The oxygen permeability of the sample was measured under the conditions of a temperature of 30 ° C. and a relative humidity of 70% using an oxygen permeation tester (OXTRAN 2/20, manufactured by Modern Control). In accordance with JIS K-7126 “B method (isobaric method)” and ASTM D3985-81, the measurement method is expressed in units of cm ³ (STP) / (m ² · day · MPa). . Here, (STP) means standard conditions (0 ° C., 1 atm) for defining the volume of oxygen.
When the measured value exceeded 1000 cm ³ (STP) / (m ² · day · MPa), the oxygen permeation tester automatically stopped, and in this case “measurement impossible” was displayed.

(Measurement of water vapor permeability)
Using a water vapor transmission tester (PERMATRAN 3/31, manufactured by Modern Control), the hydrogen permeability of the sample was measured under conditions of a temperature of 40 ° C. and a relative humidity of 90%. The measurement method described the measured value by unit: g (STP) / (m < ² > * day) based on JIS K-7129 and ASTM F1249-90.
When the measured value exceeded 20 g (STP) / (m ² · day), the water vapor permeation tester automatically stopped measuring. In this case, “measurement impossible” was displayed.

[3. Abuse resistance and retort resistance evaluation]

(3-1. Evaluation of stretch resistance)
A laminate film (configuration: laminated sheet / adhesive / LLDPE) was cut into a size of 200 mm long × 150 mm wide to prepare a sample. The sample was subjected to the following abuse test (test to evaluate abuse resistance).
As an abuse test, the sample was stretched 5% in the longitudinal direction at a speed of 100 μm / second using Tensilon manufactured by Toyo Baldwin, and the stretched state was maintained for 1 minute, and then the film was returned to the original position at the same speed. Returned and stretched.
About the sample after this abuse test, the oxygen transmission rate and the water vapor transmission rate were measured by said measuring method. The results are shown in Table 1 as oxygen permeability and water vapor permeability after “stretching”.

(3-2. Evaluation of anti-retort treatment)
Using a laminate film (configuration: laminate sheet / adhesive / Ny / adhesive / CPP), a pouch having a size of 210 mm in length and 150 mm in width with four sides as a seal portion was prepared and filled with water as the contents. . Thereafter, a retort sterilization treatment was performed at 121 ° C. for 30 minutes, and oxygen and water vapor permeability after the retort sterilization treatment were measured. The results are shown in Table 1 as oxygen permeability and water vapor permeability “after retort treatment”.

As shown in the above results, the laminated sheets of Examples 1 to 6 had high gas barrier properties in the state of the base paper. Further, the difference between the oxygen permeability and the water vapor permeability in the base paper and the values of the oxygen permeability and the water vapor permeability after stretching and after the retort treatment were small and excellent in abuse resistance and heat and humidity resistance.
On the other hand, the coating liquid used for forming the coating is composed of a polymer compound (A), at least one compound (B) selected from the group consisting of organic titanium compounds and organic zirconium compounds, and SiO of silicon compound (C). The ratio of the said compound (B) with respect to the sum total with ₂ conversion amount consists of the comparative example 1 and the comparative example 2 and polymer compound (A) which are outside the range of 3-8 mass%, an organic titanium compound, and an organic zirconium compound. Comparative Example 3 in which the ratio of the polymer compound (A) to the total of the SiO ₂ equivalent amount of at least one compound (B) selected from the group and the silicon compound (C) is out of the range of 25 to 30% by mass And Comparative Example 4, a laminated sheet of Comparative Example 5 that does not contain at least one compound (B) selected from the group consisting of an organic titanium compound and an organic zirconium compound, The difference between the value of the oxygen permeability and water vapor permeability, the value of oxygen permeability and water vapor permeability after stretching or after retorting in is large.

The laminated sheet of the present invention has a high gas barrier property even under high temperature and high humidity, and can maintain the gas barrier property at a high level even after hot water treatment such as boil treatment and retort treatment. In addition, gas barrier properties are unlikely to deteriorate even after abuse such as bending or stretching.
Therefore, by using the laminated sheet of the present invention, post-processing such as a printing process, dry lamination, melt extrusion lamination, thermocompression lamination, etc. is provided to provide a packaging material with a wide practical range used in the packaging field of foods, pharmaceuticals, etc. It is possible.

  The laminated sheet of the present invention can be used for applications other than packaging materials. Applications other than packaging materials include, for example, LCD substrate films, organic EL substrate films, electronic paper substrate films, electronic device sealing films, PDP films, LED films, IC tag films, solar cell bags Sheets, films related to electronic devices such as protective films for solar cells, optical communication members, flexible films for electronic devices, diaphragms for fuel cells, sealing films for fuel cells, substrate films for various functional films, and the like.

DESCRIPTION OF SYMBOLS 1 Base material 2 Anchor coat layer 3 Inorganic compound layer (inorganic vapor deposition layer, gas barrier layer)
5 Composition (I) Layer 10 Laminated Sheet

Claims (10)

A laminated sheet,
A substrate;
An inorganic compound layer formed on the substrate;
Provided on the inorganic compound layer, the polymer compound (A) having a hydroxyl group, at least one compound (B) selected from the group consisting of an organic titanium compound and an organic zirconium compound, and a silicon compound (C) A layer formed from a composition comprising:
A laminated sheet comprising:   The said compound (B) contains at least 1 sort (s) of compounds (B1) chosen from the group of the metal chelate compound, the hydrolyzate of the said metal chelate compound, and the condensate of the said metal chelate compound. Laminated sheet. The laminated sheet according to claim 1, wherein the silicon compound (C) includes at least one compound (C1) selected from the group consisting of a compound represented by the following formula (c1) and a hydrolyzate thereof.
Si (OR ¹ ) ₄ (c1)
(In the formula, R ¹ is an alkyl group having 1 to 4 carbon atoms or an alkoxyalkyl group having 1 to 4 carbon atoms, and four R ¹ in the formula may be the same or different.) The mass ratio between the polymer compound (A) and the total amount of the compound (B) and the compound (C1) in terms of SiO ₂ is in the range of 25/75 to 30/70. The laminated sheet according to any one of the above. The polymer compound (A), the compound (B), the ratio of said compound to the total of SiO ₂ equivalent amount of the compound (C1) (B) is from 3 to 8 wt%, claim 1 The laminated sheet as described in any one of -4.   The laminated sheet according to any one of claims 1 to 5, wherein the inorganic compound layer is a gas barrier layer composed of an inorganic material.   The packaging material containing the lamination sheet as described in any one of Claims 1-6.   The packaging material according to claim 7, which is a packaging material for hot water treatment.   A molded article comprising the packaging material according to claim 7 or 8.   The molded product according to claim 9, which is a vertical bag-filled seal bag, a vacuum packaging bag, a pouch with a spout, a laminated tube container, an infusion bag, a container lid, a paper container, or a vacuum insulator.

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