JP2000043182A - High adhesion gas barrier transparent laminate, packing material and package - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a packing material excellent in transparency, having high gas barrier properties, not deteriorating physical properties even after boiling or retorting sterilization and having high boiling resistance and retorting resistance. SOLUTION: A high adhesion gas barrier transparent laminate wherein a transparent primer layer 2 comprising trifunctional organosilane or a hydrolysate thereof, acryl polyol and an isocyanate compd., a vapor deposition membrane layer 3 with a thickness of 5-300 μm and a gas barrier composite film 4 containing metal alkoxide or a hydrolysate thereof and characterized by that the interlaminar distance of the inorg. laminar compds. in the composite film 4 is expanded by 1.2 times or more with respect to that of the inorg. laminar compds before the composite film is formed are successively laminated on a base material 1 is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate for packaging used in the field of packaging of foods, non-foodstuffs, pharmaceuticals, etc., which requires a particularly high gas barrier property and sterilizes boil, retort, and autoclave. Etc. are related to the packaging field.

[0002]

2. Description of the Related Art In recent years, packaging materials used for packaging foods, non-foodstuffs, pharmaceuticals, etc., include oxygen, water vapor, and the like which penetrate the packaging material in order to suppress deterioration of contents and maintain their functions and properties. In addition, it is necessary to prevent the influence of the gas that alters the contents, and it is required to have a gas barrier property for blocking these gases. Therefore, conventionally, a packaging material mainly using a metal foil made of a metal such as aluminum or a vapor-deposited film thereof as a gas barrier layer, which is less affected by temperature, humidity, and the like, has been generally used.

[0003] However, a packaging material using a metal foil made of a metal such as aluminum or a vapor-deposited film thereof is excellent in gas barrier properties, but the contents cannot be checked through the packaging material and the waste material after use cannot be discarded. In such a case, there is a problem in that it has to be treated as a non-combustible substance, and a metal detector cannot be used in the inspection of foreign substances and the like.

Accordingly, as a packaging material which overcomes these drawbacks, for example, US Pat.
A film obtained by forming an inorganic oxide such as silicon oxide, aluminum oxide, and magnesium oxide on a polymer film as described in -28017 and the like on a polymer film by using a vapor deposition method or a sputtering method to form a vapor-deposited film. Is being developed. These deposited films are transparent and oxygen,
It is known to have a gas barrier property against water vapor and the like, and is considered to be suitable as a packaging material having both transparency and gas barrier properties that cannot be obtained with metal foil or the like.

[0005]

However, even a film suitable for the above-mentioned packaging material is rarely used alone as a vapor deposition film as a packaging container or a packaging material. A package is completed through various processes such as printing or laminating characters and pictures on the surface or laminating the film with a film or the like, and shape processing into a package such as a container. In particular, packaging materials used for boil sterilization, retort sterilization, autoclave sterilization, and the like are sterilized through various processes. Therefore, sufficient attention must be paid to the design of the packaging materials.

[0006] Then, after laminating a bag with a sealant film using the above-mentioned vapor-deposited film or the like, filling the contents and performing sterilization by boiling or retort, delamination occurs in a part of the seal portion after sterilization. In addition, there were problems such as poor appearance and deterioration of the gas barrier property from the portion to deteriorate the contents.

In other words, the conditions used as a packaging material in such a case include transparency that allows the contents to be directly seen through, high gas barrier properties that block gases that affect the contents, and the like. Boil sterilization and retort sterilization, there is no deterioration of gas barrier properties even after autoclave sterilization, and also it is required to have boil resistance, retort resistance and autoclave resistance such that delamination does not occur in the seal portion and the like, At present, no packaging material that meets all of these has been found.

[0008] Therefore, in the present invention, excellent transparency,
It is another object of the present invention to provide a highly practical packaging material having high gas barrier properties and high boil resistance and retort resistance without physical property deterioration even after boil sterilization or retort sterilization.

[0009]

The present invention achieves the above object.
The invention described in claim 1 is transparent.
At least one side of a substrate made of a plastic material
General formula R'Si (OR) _Three (R ′: alkyl group, vinyl
Group, functional group such as glycidoxypropyl group, R: C_nH
_{2n + 1}Alkyl group (_n: An integer greater than or equal to 1)
Functional organosilane or hydrolyzation of the organosilane
Decomposed product, acrylic polyol and isocyanate compound
A transparent primer layer composed of a composite with
nm inorganic oxide deposited thin film layer, furthermore aqueous polymer
And inorganic layer compound and general formula M (OR)_n(M: metal source
Elementary, R: C_nH_{2n + 1}Alkyl group (_n: 1 or more
Number)) or its hydrolysis
And a gas barrier composite coating comprising:
The interlayer distance of the inorganic layered compound of the
1.2 times larger than the interlayer distance of the layered compound
Gas barrier composite coating layer
It is a strong adhesion gas barrier transparent laminate.

In this case, the number of _n may be different for each group or may be the same. However, when a C _n H _{2n + 1} alkyl group is indicated,
The value of _n in the value and H _{2n + 1} of the _n in the _n is a display for an alkyl group display, but the same value, _n in the in C _n H _{2n + 1} in the organosilane value and the value of _n in C _n H _{2n + 1} in the metal alkoxide and shall not necessarily the same value of _n.

Further, the invention of claim 2 is based on the invention of claim 1, wherein an epoxy group is contained in R ′ constituting the trifunctional organosilane. Is a highly adherent gas barrier transparent laminate.

According to a third aspect of the present invention, there is provided a strongly adhered gas barrier transparent laminate according to the first or second aspect, wherein a reaction catalyst is added to the composite.

According to a fourth aspect of the present invention, based on the third aspect of the present invention, there is provided a strongly adhered gas barrier transparent laminate, wherein the reaction catalyst is a tin compound.

According to a fifth aspect of the present invention, based on the third and fourth aspects, the tin compound is tin chloride, tin oxychloride and tin alkoxide. .

According to a sixth aspect of the present invention, based on the first to fifth aspects, the compound represented by the general formula M (OR) _n
(M: metal element, R: alkyl group of C _n H _{2n + 1} , _n : 1
A strongly adhered gas barrier transparent laminate characterized by adding a metal alkoxide or a hydrolyzate thereof represented by the above integer). In this case, the number of _n may be different from the value of _n shown in claim 1 for each base or may be the same.

According to a seventh aspect of the present invention, based on the first to sixth aspects, the metal element in the metal alkoxide or the hydrolyzate of the metal alkoxide is Si, Al,
A strongly adhered gas barrier transparent laminate characterized by being Ti, Zr or a mixture thereof.

The invention of claim 8 is based on the invention of claims 1 to 7, wherein the thickness of the transparent primer layer is 0.01 to 0.01.
A strongly adhered gas barrier transparent laminate having a range of 2 μm.

According to a ninth aspect of the present invention, there is provided a strongly adhered gas barrier transparent laminate according to the first to eighth aspects, wherein the laminate is a simple substance of aluminum oxide, silicon oxide, magnesium oxide or a mixture thereof.

According to a tenth aspect of the present invention, based on the first to ninth aspects, the interlayer distance of the inorganic layered compound in the gas barrier composite coating is the interlayer distance of the inorganic layered compound alone before the formation of the composite coating. A strongly adhered gas barrier transparent laminate characterized in that the size of the transparent laminate is at least twice as large as that of the transparent laminate.

The invention of claim 11 is based on the invention of claims 1 to 10, wherein the metal alkoxide is tetraethoxysilane or triisopropoxyaluminum;
Alternatively, it is a strong adhesion gas barrier transparent laminate characterized by being a mixture thereof.

According to a twelfth aspect of the present invention, based on the first to eleventh aspects, the aqueous polymer is a polyvinyl alcohol, wherein the aqueous polymer is polyvinyl alcohol.

A thirteenth aspect of the present invention is the strongly adhered gas barrier laminate according to any one of the first to twelfth aspects, wherein the inorganic layered compound is a smectite group inorganic layered compound.

According to a fourteenth aspect, based on the thirteenth aspect, the smectite group inorganic layered compound comprises:
A strongly adhered gas barrier laminate characterized by being montmorillonite.

According to a fifteenth aspect of the present invention, there is provided the strongly adhered gas barrier laminate according to any one of the first to fourteenth aspects, wherein a printed layer is provided.

According to a sixteenth aspect of the present invention, there is provided a packaging material comprising a gas barrier laminate according to any one of the first to fifteenth aspects, wherein an intermediate layer is laminated on the composite film forming surface. .

According to a seventeenth aspect of the present invention, there is provided a packaging material characterized in that a heat seal layer is laminated on the composite coating forming surface of the gas barrier laminate according to any one of the first to sixteenth aspects. is there.

The invention of claim 18 is characterized in that a packaging material base is laminated on the surface of the substrate of the gas barrier laminate according to any one of claims 1 to 17 opposite to the surface on which the composite coating is formed. Packaging material.

According to a nineteenth aspect of the present invention, there is provided a package obtained by bag-making the packaging material according to any one of the first to eighteenth aspects.

[0029] The twentieth aspect of the present invention is the package according to the eighteenth and nineteenth aspects obtained by heat-sealing the heat-sealing resin of the packaging material according to the eighteenth aspect to form a bag.

According to the present invention, after providing a transparent primer layer having excellent dimensional stability and adhesion even after sterilizing boil or retort on a transparent plastic substrate, an inorganic oxide layer and a gas barrier having excellent gas barrier properties are provided. The functional composite coating layer is sequentially laminated, so that a highly practical laminate without delamination (peeling of the laminated part) and deterioration of gas barrier properties even after boil sterilization or retort sterilization is obtained. Can be

[0031]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in more detail with reference to the drawings. FIG. 1 is a cross-sectional view illustrating a strongly adhered gas barrier transparent laminate of the present invention.

First, the strongly adhered gas barrier transparent laminate of the present invention shown in FIG. 1 will be described. The substrate 1 in FIG. 1 is a film made of a transparent plastic material, on which a transparent primer layer 2 made of a complex of a trifunctional organosilane and an acrylic polyol, an isocyanate compound, etc., and a vapor-deposited thin film layer made of an inorganic oxide 3. A gas barrier composite coating layer 4 composed of a composite such as an aqueous polymer, an inorganic layer compound, and a metal alkoxide is sequentially laminated.

The above-mentioned substrate 1 is a transparent plastic material, and is preferably a transparent film in order to make use of the transparency of the primer layer 2, the deposited thin film layer 3, and the gas barrier composite coating layer 4. For example, polyethylene terephthalate (PE
T), polyester films such as polyethylene naphthalate, polyolefin films such as polyethylene and polypropylene, polystyrene films, polyamide films, polyvinyl chloride films, polycarbonate films, polyacrylonitrile films, polyimide films and the like are used. Either is fine,
Those having mechanical strength and dimensional stability are preferred. These are processed into a film and used. Particularly, polyethylene terephthalate arbitrarily stretched in the biaxial direction is preferably used. In addition, various known additives and stabilizers, for example, an antistatic agent, an ultraviolet ray inhibitor, a plasticizer, a lubricant, and the like may be used on the surface of the substrate 1 in order to improve the adhesion to the thin film. Further, a corona treatment, a low-temperature plasma treatment, an ion bombardment treatment or a chemical treatment, a solvent treatment or the like may be applied as a pretreatment.

Although the thickness of the substrate 1 is not particularly limited, it is suitable as a packaging material, there may be cases where other layers are laminated, the transparent primer layer 2 and the inorganic oxide deposited thin film layer 3, In consideration of the workability when forming the gas barrier coating layer 4, in a practical range of 3 to 200 μm,
It is preferably 6 to 30 μm depending on the application.

Further, in consideration of mass productivity, it is desirable to use a long film so that each layer can be formed continuously.

The transparent primer layer 2 of the present invention is provided on a substrate 1 made of a transparent plastic material, and enhances the adhesion between the substrate 1 and the deposited thin film layer 3 made of an inorganic oxide.
An object of the present invention is to prevent boil sterilization, retort sterilization, and delamination occurring in a seal portion after autoclave sterilization.

As a result of intensive studies, it is necessary to use a composite of an organosilane having three functional groups or a hydrolyzate thereof, an acrylic polyol, an isocyanate compound and the like to be used as a primer resin in order to achieve the above object. There is.

The above composite will be described in more detail.
The trifunctional organosilane is a general formula R'Si (OR) such as ethyltrimethoxysilane, vinyltrimethoxysilane, and glycidoxypropyltrimethoxysilane.
₃ (R ′ is a functional group such as an alkyl group, a vinyl group and a glycidoxypropyl group; R: an alkyl group represented by the general formula C _n H _{2n + 1} such as CH ₃ and C ₂ H ₅ ( _n : 1 or more ) Or a hydrolyzate thereof. As a method for obtaining the hydrolyzate, a well-known method obtained by directly adding an acid, an alkali, or the like to the trifunctional organosilane can be used. Among them, glycidoxytrimethoxysilane or epoxycyclohexylethyltrimethoxysilane in which an epoxy group is contained in R ′ is particularly preferable because of its excellent physical properties.

The acrylic polyol is a polymer compound obtained by polymerizing an allylic acid derivative monomer or a polymer compound obtained by copolymerizing an acrylic acid derivative monomer and other monomers, having a hydroxyl group at a terminal. It reacts with isocyanate groups in the isocyanate compound to be added later. Among them, those obtained by polymerizing acrylic acid derivative monomers such as ethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxylbutyl methacrylate alone, and acrylic polyols obtained by adding and copolymerizing other monomers such as styrene are preferably used. In consideration of the reactivity with the isocyanate compound, the hydroxyl value is 5 to 200 (KOHm
g / g).

The mixing ratio of the acrylic polyol and the trifunctional organosilane is preferably in the range of 1/1 to 100/1 in terms of weight ratio, more preferably 2/1 to 50.
/ 1 range. The dissolving and diluting solvent is not particularly limited as long as it can be dissolved and diluted, for example, esters such as ethyl acetate / butyl acetate, alcohols such as methanol / ethanol / isopropyl alcohol, ketones such as methyl ethyl ketone,
Aromatic hydrocarbons such as toluene and xylene and the like may be used alone or in any combination. Above all,
Since an aqueous solution of hydrochloric acid or the like may be used to hydrolyze the trifunctional organosilane or the like, it is more preferable to use a mixture of isopropyl alcohol or the like and a polar solvent of ethyl acetate arbitrarily as a co-solvent.

A reaction catalyst may be added to promote the reaction when the trifunctional organosilane and the acrylic polyol are blended. As a catalyst to be added, tin chloride (SnCl ₂ , Sn
Cl ₄ ), tin oxychloride (SnOHCl, Sn (OH)
It is preferably a tin compound such as ₂ Cl ₂ ) or tin aquoxide. Since the catalytic effect cannot be obtained if the amount is too small or too large, it is preferably in the range of 1/10 to 1/10000, more preferably 1 to 1 in terms of molar ratio with respect to the trifunctional organosilane. / 100 to 1/2000.

The isocyanate compound to be further mixed is
It is added to increase the adhesion between the substrate and the inorganic oxide layer by urethane bonds formed by reacting with the acrylic polyol, and mainly acts as a crosslinking agent or a curing agent. Examples of the isocyanate compound that can be used to achieve this include aromatic tolylene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI), aliphatic xylene diisocyanate (XDI), and hexaylene diisocyanate (HMDI).
Such monomers and polymers and derivatives thereof are used, and these are added alone or as a mixture.

The mixing ratio of the acrylic polyol and the isocyanate compound is not particularly limited. However, if the amount of the isocyanate compound is too small, the curing may be poor, and if the amount is too large, blocking or the like may occur and processing problems may occur. There is. Therefore, the compounding ratio of the acrylic polyol and the insocyanate compound is preferably such that the NCO group derived from the isocyanate compound is 50 times or less in terms of equivalent weight with respect to the OH group derived from the acrylic polyol, and particularly preferred is the NCO group and the OH group. The groups are blended in equivalent amounts. As the mixing method, a known method can be used and is not particularly limited.

Further, in order to improve the stability of the mixture during the preparation of the mixture, a metal alkoxide or a hydrolyzate thereof may be added. The metal alkoxide is tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ),
Tripropoxy aluminum (Al (OC ₃ H ₇ ) ₃ )
General formula M (OR) _n (M: metal element, R: CH ₃ ,
An alkyl group represented by the general formula C _n H _{2n + 1} such as C ₂ H ₅ ) or a hydrolyzate thereof. Among them, tetraethoxysilane, tripropoxyaluminum or a mixture of both is preferable because it is relatively stable in an aqueous solvent. As a method for obtaining the hydrolyzate of the metal alkoxide, hydrolysis may be performed together with the trifunctional organosilane, or an acid or the like may be added alone and then added.

The coating layer of the composite is obtained by directly or previously hydrolyzing such a trifunctional organosilane or by hydrolyzing with a metal alkoxide (at this time, the above-mentioned reaction catalyst or the like is added together). May be mixed with an acrylic polyol or an isocyanate compound to prepare a composite solution, or a trifunctional organosilane and an acrylic polyol are mixed in a solvent in advance (at this time, the reaction catalyst, metal It does not matter which alkoxide is added together.) The one that has undergone a hydrolysis reaction, and the one that only has a mixture of trifunctional organosilane and acrylic polyol (at this time, the reaction catalyst and metal alkoxide described above are added together. The composite liquid is prepared by adding an isocyanate compound to Coating to be formed.

Various additives such as 3
Curing accelerators such as quaternary amines, imidazole derivatives, carboxylic acid metal salt compounds, quaternary ammonium salts, and quaternary phosphonium salts; phenol-based, sulfur-based, phosphite-based antioxidants, leveling agents, and flow regulators Addition of a filler or the like is also acceptable.

The thickness of the transparent primer layer 2 is not particularly limited as long as a uniform coating film can be formed, but is generally preferably in the range of 0.01 to 2 μm. When the thickness is less than 0.01 μm, it is difficult to obtain a uniform coating film, and the adhesion may be reduced. On the other hand, if the thickness exceeds 2 μm, it is not preferable because the film cannot keep flexibility because of the thickness and there is a possibility that the film may be cracked by external factors. Particularly preferred is 0.03-
It is within the range of 0.5 μm.

The method for forming the transparent primer layer 2 is as follows.
For example, a known printing method such as an offset printing method, a gravure printing method, or a silk screen printing method, or a known coating method such as a roll coat, a knife edge coat, or a gravure coat can be used. The drying conditions may be those generally used. In order to promote the reaction, it is also possible to leave the mixture in a high-temperature aging chamber or the like for several days.

The thin film layer 3 made of an inorganic oxide is made of a deposited film of an inorganic oxide such as aluminum oxide, silicon oxide, tin oxide, magnesium oxide, or a mixture thereof.
Any material may be used as long as it has transparency and gas barrier properties such as oxygen and water vapor. Among them, aluminum oxide, silicon oxide, and magnesium oxide are particularly preferable. However, the thin film layer 3 of the present invention is not limited to the above-mentioned inorganic oxide, but may be any material that meets the above conditions.

The optimum conditions for the thickness of the thin film layer 3 vary depending on the type and constitution of the inorganic compound used.
The range is desirably in the range of ~ 300 nm, and the value is appropriately selected. However, if the film thickness is less than 5 nm, a uniform film may not be obtained or the film thickness may not be sufficient, and the function as a gas barrier material may not be sufficiently achieved. On the other hand, if the thickness exceeds 300 nm, flexibility cannot be maintained in the thin film, and the thin film may be cracked by external factors such as bending and pulling after the film is formed. Preferably, it is in the range of 10 to 150 nm.

There are various methods for forming the thin film layer 3 made of an inorganic oxide on the transparent primer layer 2, which can be formed by a usual vacuum deposition method. An ion plating method, a plasma vapor deposition method (CVD), or the like can also be used. However, in consideration of productivity, the vacuum deposition method is currently the most excellent. As a heating means of a vacuum deposition apparatus by a vacuum deposition method, an electron beam heating method, a resistance heating method,
An induction heating method is preferable, and a plasma assist method or an ion beam assist method can be used to improve the adhesion between the thin film and the substrate and the denseness of the thin film. In addition, in order to increase the transparency of the deposited film, reactive deposition in which oxygen gas or the like is blown in the deposition may be used.

The gas barrier composite coating layer 4 is provided on the inorganic oxide thin film layer 3 and is provided to provide a high gas barrier property equivalent to that of a metal foil such as aluminum.

In order to achieve the above object, the gas-barrier composite coating layer 4 includes a water-soluble polymer and an inorganic layered compound and a general formula M (OR) _n (M: metal element, R: CH ₃ ,
It must be a coating layer comprising a composite solution containing a metal alkoxide represented by the general formula C _n H _{2n + 1} such as C ₂ H ₅ ) and a hydrolyzate thereof. The interlayer distance of the inorganic layered compound needs to be 1.2 times or more (more preferably, 2 times or more) larger than the interlayer distance of the inorganic layered compound alone before the film is formed. Such a coating layer is formed by directly coating the prepared composite solution on the inorganic oxide thin film layer 3 and drying by heating.

The interlayer distance can be calculated by determining the bottom reflection (001 plane) of the inorganic layered compound in the composite coating by X-ray diffraction. That is, according to the calculation based on the X-ray diffraction method, the interlayer distance of the above-mentioned inorganic layered compound before the preparation of the composite solution varies depending on the type of the inorganic layered compound, but is usually 7 to 15 °. On the other hand, the interlayer distance of the inorganic layered compound after the preparation of the composite solution in the present invention is 1.2 times or more thereof, and those having more preferable high gas barrier properties are twice or more thereof.

In the present invention, the inorganic layered compound and the water-soluble polymer and the metal alkoxide are not simply mixed and dispersed in the composite coating, but the water-soluble polymer and the metal alkoxide are interposed between the layers of the inorganic layered compound. The inorganic layered compound and the water-soluble polymer or metal alkoxide are complexed at the molecular level. For this reason, it is considered that the composite coating has high gas barrier properties and can suppress humidity deterioration and temperature dependence.

The composite coating will be described in more detail. The water-soluble polymer used for the composite coating in the present invention is not particularly limited as long as it is water-soluble and easily penetrates into the layers of the layered compound from the viewpoint of compatibility with the inorganic layered compound and the metal alkoxide. System, starch
Alcohols such as methylcellulose and carboxymethylcellulose, and acrylic polyols can be used. Considering gas barrier properties, polyvinyl alcohol is more preferable.

The above polyvinyl alcohol (hereinafter referred to as PVA)
) Is generally obtained by saponifying polyvinyl acetate, and includes so-called partially saponified PVA in which acetic acid groups remain tens of percent, to complete PVA in which only a few percent of acetic acid groups remain. Is not particularly limited.

The inorganic layered compound used in the composite coating means a crystalline inorganic compound having a layered structure, for example, a viscous mineral represented by a kaolinite group, a smectite group or a mica group. it can. As long as the compound is an inorganic layered compound, its type, particle size, aspect ratio, and the like can be appropriately selected depending on the desired required quality and the like, and are not particularly limited. In general, a smectite group inorganic layered compound is suitable in that a water-soluble polymer component or a metal alkoxide component enters between layers of the layered structure, and a composite film in which the layers are enlarged is easily obtained. Specific examples of the smectite group include montmorillonite, hectorite, saponite and the like.
Montmorillonite is more preferable from the viewpoints of stability in solution, coatability and the like.

The metal alkoxide is a general formula such as tetraethoxysilane [Si (OC ₂ H ₅ ) ₄ ] or triisopropoxy aluminum [Al (OC ₃ H ₇ ) ₃ ], M (OR) _n (M: Metal element, R: CH ₃ , C ₂ H
An alkyl group represented by the general formula C _n H _{2n + 1} such as _5, or a hydrolyzate thereof. Among them, tetraethoxysilane and triisopropoxyaluminum are preferable because they are relatively stable in an aqueous solvent after hydrolysis.

As a method for adjusting these three components, a known adjustment method or the like can be used, and there is no particular limitation. The blending ratio varies depending on the required quality, but is generally 25 to 45: 1 to 1 by weight in terms of a water-soluble polymer: an inorganic layered compound: a metal alkoxide and a hydrolyzate thereof.
5: It is appropriately selected in the range of 40 to 80. Considering gas barrier properties and flexibility, more preferably 3
0 to 40: 1 to 5:50 to 70.

In the formation of this composite coating, the interlayer distance of the inorganic layered compound in the composite coating is adjusted by the combination of the inorganic layered compound to be used and the water-soluble polymer / metal alkoxide, the mixing ratio, the heating temperature during mixing, and the like. Can be performed appropriately.

Further, other components can be added to the composite coating as long as the physical properties are not impaired. For example, an isocyanate compound, a silane coupling agent, or a dispersant, a stabilizer, a viscosity modifier, a coloring agent, and the like.

As a method for applying the coating agent, conventionally known means such as a commonly used dipping method, roll coating method, screen printing method, spraying method and the like can be used. The thickness of the coating varies depending on the type of coating agent and processing conditions, but the thickness after drying is 0.01μ.
It is sufficient that the thickness is at least m, but if the thickness is at least 50 μm, cracks are likely to occur in the film.

Further, another layer can be laminated on the inorganic oxide thin film layer 3 and the gas barrier coating layer 4. For example, it is a printing layer, an intermediate layer, a heat seal layer, or the like. The printing layer is formed for practical use as a packaging bag or the like, and is a urethane type, an acrylic type, a nitrocellulose type,
It is a layer composed of ink obtained by adding various pigments, extender pigments and additives such as plasticizers, drying agents and stabilizers to conventionally used ink binder resins such as rubber-based and vinyl chloride-based. , Characters, pictures, etc. are formed. As a forming method, for example, a well-known printing method such as an offset printing method, a gravure printing method, or a silk screen printing method, or a well-known coating method such as a roll coat, a knife edge coat, or a gravure coat can be used. The thickness may be 0.1 to 2.0 μm.

The intermediate layer is boiled and autoclaved,
It is provided to increase the bag breaking strength during retort sterilization, etc., and generally from among biaxially stretched nylon film, biaxially stretched polyethylene terephthalate film, and biaxially stretched polypropylene film in terms of mechanical strength and thermal stability. It needs to be the kind of choice. The thickness is determined according to the material, required quality, and the like.
The range is 0 μm. As a forming method, laminating can be performed by a known laminating method such as a dry laminating method of laminating via a two-component curable urethane-based adhesive.

The heat seal layer is used for an adhesive portion when forming a bag-like package or the like. For example, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methacrylic acid copolymer, Ethylene-
Resins such as methacrylic acid ester copolymers, ethylene-acrylic acid copolymers, ethylene-acrylic acid ester copolymers, and cross-linked metals thereof are used. The thickness is determined according to the purpose, but is generally in the range of 15 to 200 μm. As a forming method, a method of laminating a film-like material made of the above resin by a dry laminating method of bonding using an adhesive such as a two-component curable urethane resin, or a non-solvent laminating method of bonding by using a non-solvent adhesive is used. Any of known methods such as an extrusion lamination method in which the above-described resin is heated and melted, and extruded and pasted in a curtain shape can be used.

Further, a configuration in which a layer other than the above layers is provided may be employed. For example, a configuration in which a transparent layer having a primer effect is provided in contact with or separately from the transparent primer layer as described above may be used. Similarly, the inorganic vapor-deposited layer may be a layer having two or more layers having substantially different composition ratios or a layer having a continuously changing composition. Not limited to the transparent primer layer or the inorganic vapor-deposited layer, the constitution does not need to be uniform in other layers, and the layers described have substantially different composition ratios or the like. May be regarded as a layer in which the temperature changes.

If these requirements are satisfied only with this gas barrier laminate in terms of strength and design, it may be used alone as a packaging material. However, the packaging material may be provided on the opposite side of the substrate from the surface on which the gas barrier coating layer is formed. A configuration in which strength and the like are provided by a configuration in which material bases are laminated is also conceivable.

As the packaging material base, specifically, paper,
It is a base material such as polyethylene, polypropylene, polyester, polyamide, and non-woven fabric. The thickness is not particularly limited.

The bag making method using such a packaging material includes a horizontal pillow, a vertical pillow, a gusset, a four-side seal,
A package is made by appropriately selecting from a bag making method such as a three-sided seal, etc.In order to maintain the gas barrier property of the completed packaging material, the bag is formed by heat sealing, which exhibits gas barrier properties even at seams In many cases, a package obtained by the above method is preferable.

[0071]

EXAMPLES The transparent gas-barrier laminate of the present invention will be further described with reference to specific examples.

<Preparation of Composite Solution for Transparent Primer Layer> A) Tetraethoxysilane ([Si (OC ₂ H ₅ )
₄ ]: A solution of tin chloride (SnCl ₂ ) / methanol as a catalyst in 1/4 of TEOS) and epoxycyclohexylethyltrimethoxysilane (hereinafter abbreviated as EETMS).
Then, 0.1N hydrochloric acid was added to a mixture obtained by adding 00 mol and mixing them at a molar ratio of 1: 1.
Acrylic polyol is further added at a weight ratio of 5: 1 with respect to the total of TEOS and EETMS and stirred, and then tolylene diisocyanate (hereinafter abbreviated as TDI) as an isocyanate compound is added to the OH group of the acrylic polyol. And a diluting solvent was added thereto to obtain a composite solution A.

B) Tin chloride (Sn
A Cl ₂ ) / methanol solution was added in an amount of 1/135 mol, and an acrylic polyol was further added thereto in a weight ratio of 5: 1 with respect to EETMS, followed by stirring.
The NCO group was added in an amount equivalent to the H group, and a diluting solvent was added to obtain a composite solution B.

C) TDI as an isocyanate compound was added to the acrylic polyol so that the NCO group was equivalent to the OH of the acrylic polyol, and a diluting solvent was added to obtain a composite solution C.

<Preparation of Composite Solution for Gas Barrier Coating Layer> 1) A hydrolyzate of montmorillonite as an inorganic layered compound, a polyvinyl alcohol as a water-soluble polymer and a tetraethoxysilane as a metal alkoxide were added in a weight ratio of 35. : 3:62, and a diluting solvent was added to obtain a composite solution.

2) A composite solution was obtained in the same manner except that the weight ratio of the three was mixed to 35:10:55.

3) A composite solution was obtained in the same manner except that muscovit was used as the inorganic layer compound in the composite solution.

<Example 1> As the substrate 1, a thickness of 12 μm
A composite solution A was formed as a transparent primer layer 2 on one surface of a biaxially stretched polyethylene terephthalate (PET) film having a thickness of 0.1 μm by a gravure coating method. Next, metallic aluminum is evaporated on the transparent primer layer 2 by an electron beam heating type vacuum evaporation apparatus (not shown), and oxygen gas is introduced therein to deposit aluminum oxide having a thickness of about 20 nm to form the inorganic oxide thin film layer 3. Formed. Furthermore, a composite solution having a thickness of 0.5 μm was formed thereon as a gas barrier composite coating layer 4 by a gravure coating method to obtain a strongly adhered gas barrier transparent laminate of the present invention.

<Example 2> A strongly adhered gas barrier transparent laminate of the present invention was obtained in the same manner as in Example 1, except that the composite solution B was used as the transparent primer layer 2.

<Example 3> In Example 1, except that silicon oxide having a thickness of about 40 nm was deposited as the inorganic oxide thin film layer 3 by a vacuum deposition apparatus using a resistance heating method (not shown). An adhesive gas barrier transparent laminate was obtained.

Example 4 A strongly adhered gas barrier transparent laminate of the present invention was obtained in the same manner as in Example 1, except that the deposition was carried out after being left in an aging chamber at 50 ° C. for 2 days.

<Example 5> In Example 1, except that a composite solution was used as the gas barrier composite coating layer 4,
Similarly, a strongly adhered gas barrier transparent laminate of the present invention was obtained.

Example 6 A strongly adhered gas barrier transparent laminate of the present invention was obtained in the same manner as in Example 5, except that the composite solution B was used as the transparent primer layer 2.

Comparative Example 1 A transparent laminate of the present invention was obtained in the same manner as in Example 1, except that the composite solution C was used as the transparent primer layer 2.

<Comparative Example 2> In Example 1, except that a composite solution was used as the gas barrier composite coating layer 4,
Similarly, a transparent laminate was obtained.

Comparative Example 3 A transparent laminate was obtained in the same manner as in Example 1, except that the transparent primer layer 2 was not formed.

Comparative Example 4 A transparent laminate was obtained in the same manner as in Example 1, except that the gas barrier composite coating layer 4 was not formed.

<Evaluation of Laminate> For each of the laminates of Examples and Comparative Examples, (1) interlayer distance expansion rate, (2) oxygen permeability (cc / m ² / day), and (3) water vapor permeability (gr) /
m ² / day), (4) transparency, and (5) incineration were evaluated. Table 1 shows the results.

(1) Magnification of interlayer distance X-ray diffraction analyzer (X-ray source: CuKα, output: 100 k)
w), the 001 reflection peak profile was measured, the center d value (half value d value) of the half value position of the maximum peak was calculated to determine the interlayer distance, and the magnification was measured using the following equation. Interlayer distance expansion rate = interlayer distance of composite layer / interlayer distance of inorganic layered compound alone

(2) Oxygen Permeability Oxygen Permeability Measurement System (OXTR, Modern Control Company)
AN-10 / 50A) at 30 ° C. and 70% RH in an atmosphere.

(3) Water Vapor Permeability Water Vapor Permeability Measurement Apparatus (PER, Modern Control Co., Ltd.)
MATRAN-W / W31) at 40 ° C-90%
It was measured under an atmosphere in RH.

(4) Transparency The laminate was visually examined to see if the shape of the contents and the like could be confirmed.

(5) Incineration property A combustion test was performed, and the presence or absence of incombustible substances was visually evaluated.

<Dry Lamination> A 15 μm-thick intermediate layer was formed on the gas-barrier composite coating layer side of each of Examples and Comparative Examples.
m biaxially stretched nylon film is laminated by a dry lamination method via a two-component curable urethane adhesive, and a 60 μm thick polypropylene film is further dried as a heat seal layer via a two-component curable urethane adhesive. Lamination was performed by a lamination method.

<Evaluation of retort suitability> In order to evaluate the retort suitability of the above-mentioned laminate, each four-side seal pouch was prepared and filled with 150 g of water as a content.
Retort sterilization was performed at 25 ° C. for 30 minutes. As the evaluation of retort aptitude, the oxygen permeability before and after retort (cc / m
² / day) and laminate strength (gr / 15 mm),
Furthermore, the occurrence of delamination in the seal after the retort was observed by visual observation. Table 1 also shows the results.

[0096]

[Table 1]

In contrast to the embodiment, the comparative example was set under the conditions used as the above-described packaging material, and was transparent enough to allow the contents to be directly seen through, and shielded from gases that affect the contents. Even after high gas barrier properties and various sterilizations (such as boil, retort, and autoclave), the gas barrier properties are not deteriorated and the various sterilization resistances without delamination are not satisfied. However, the examples satisfy all of them. It can be said.

[0098]

As described above, according to the present invention, it is possible to obtain a versatile packaging material having excellent transparency and a high gas barrier property comparable to that of aluminum foil. Since it has excellent suitability for boiling, retorting and auto-flaving, it can be widely used in the packaging field.

[0099]

[Brief description of the drawings]

FIG. 1 is a partial cross-sectional view of a strongly adhered gas barrier transparent laminate of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Transparent plastic base material 2 Transparent primer layer 3 Inorganic oxide thin film layer 4 Gas barrier composite coating layer

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tomonori Komori 1-5-1, Taito, Taito-ku, Tokyo Inside Toppan Printing Co., Ltd. (72) Inventor Ryuyoshi Matsuo 1-1-5-1 Taito, Taito-ku, Tokyo F-term in Toppan Printing Co., Ltd. (Reference) 3E086 AC07 AD01 BA15 BA24 BA33 BA35 BA40 BB01 BB22 BB41 BB51 CA03 CA28 4F100 AA01E AA05C AA17D AA18D AA19D AA20D AA28C AH02C AH06B AK01A31A01 BAKCA JB05E JD02 JD02E JK06 JL12 JL12E JN01 JN01A

Claims (20)

[Claims] 1. A substrate made of a transparent plastic material, on at least one surface of which a general formula R'Si (OR) ₃ (R ': a functional group such as an alkyl group, a vinyl group or a glycidoxypropyl group, R: C _n A transparent primer layer comprising a trifunctional organosilane represented by an alkyl group of H _{2n + 1} ( _n : an integer of 1 or more) or a hydrolyzate of the organosilane, and a composite of an acrylic polyol and an isocyanate compound; Vapor-deposited thin film layer made of an inorganic oxide having a thickness of 5 to 300 nm, an aqueous polymer, an inorganic layered compound, and a compound of the general formula M (O
R) _n (M: metal element, R: alkyl group of C _n H _{2n + 1} (
_n : an integer of 1 or more) In a gas barrier composite coating containing a metal alkoxide or a hydrolyzate thereof represented by the following formula, the interlayer distance of the inorganic layered compound in the composite coating is the interlayer distance of the inorganic layered compound before the formation of the composite coating. 1.2 for
A strongly adhered gas barrier transparent laminate characterized by sequentially laminating a gas barrier composite coating layer that has been doubled in size. 2. The strongly adherent gas barrier transparent laminate according to claim 1, wherein an epoxy group is contained in R ′ constituting said trifunctional organosilane. 3. The strongly adherent gas barrier transparent laminate according to claim 1, wherein a reaction catalyst is added to the composite. 4. The strongly adherent gas barrier transparent laminate according to claim 3, wherein the reaction catalyst is a tin compound. 5. The strongly adherent gas barrier transparent laminate according to claim 3, wherein the tin compound is tin chloride, tin oxychloride and tin alkoxide. 6. A compound of the general formula M (OR)
_{2. A} metal alkoxide represented by _n (M: a metal element, R: an alkyl group of C _n H _{2n + 1} ( _n : an integer of 1 or more)) or a hydrolyzate thereof is added. 6. The strongly adhered gas barrier transparent laminate according to any one of items 1 to 5. 7. The method according to claim 7, wherein the metal element in the metal alkoxide or the hydrolyzate of the metal alkoxide is Si, Al, T
7. The strongly adherent gas barrier transparent laminate according to claim 1, wherein the transparent laminate is i, Zr, or a mixture thereof. 8. The transparent primer layer having a thickness of 0.01
8. The method according to claim 1, wherein the distance is in the range of 2 to 2 [mu] m.
The strongly adherent gas barrier transparent laminate according to any one of the above. 9. The strongly adhered gas barrier transparent laminate according to claim 1, wherein said inorganic oxide is aluminum oxide, silicon oxide, magnesium oxide alone or a mixture thereof. 10. The method according to claim 1, wherein the interlayer distance of the inorganic layered compound in the gas barrier composite coating is twice or more as large as the interlayer distance of the inorganic layered compound alone before the composite coating is formed. The strongly adhered gas barrier transparent laminate according to claim 1. 11. The strongly adherent gas barrier transparent laminate according to claim 1, wherein the metal alkoxide is tetraethoxysilane, triisopropoxyaluminum, or a mixture thereof. 12. The strongly adhered gas barrier transparent laminate according to claim 1, wherein the aqueous polymer is polyvinyl alcohol. 13. The strongly adhered gas barrier laminate according to claim 1, wherein said inorganic layered compound is a smectite group inorganic layered compound. 14. The smectite group inorganic stratiform compound is montmorillonite.
4. The strongly adhered gas barrier laminate according to 3. 15. The strongly adherent gas barrier laminate according to claim 1, further comprising a printed layer. 16. A packaging material, wherein an intermediate layer is laminated on the composite coating forming surface of the gas barrier laminate according to any one of claims 1 to 15. 17. A packaging material, wherein a heat seal layer is laminated on the composite coating forming surface of the gas barrier laminate according to any one of claims 1 to 16. 18. A gas barrier laminate according to any one of claims 1 to 17, wherein the substrate has a surface opposite to the composite film forming surface,
A packaging material characterized by laminating a packaging material base. 19. A package obtained by bag-making the packaging material according to claim 1. 20. The package according to claim 18, which is obtained by heat-sealing the heat-sealing resin of the packaging material according to claim 18 to form a bag.