JP2000127300A - Strongly adhering gas barrier transparent laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a packaging material, excellent in transparency, having high gas barrier property as well as high adhesive property, not being deteriorated in the physical property even after boil sterilization or retort sterilization, having high resistance to boiling as well as resistance to retort without generating any separating phenomenon or the like and high in the practical use of the same. SOLUTION: A strongly adhering gas barrier transparent laminate is formed by a method wherein a transparent primer layer 2, consisting of a composite of an acrylic polyol, a polyester polyol, an isocyanate compound and a silane coupling agent, and a deposit thin film layer 3, having the thickness of 5-300 nm and constituted of an inorganic oxide, are laminated sequentially on at least one side of a substrate 1 made of a transparent plastic material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a packaging laminate used in the field of packaging foods, non-foods, pharmaceuticals, etc., and more particularly to the field of packaging which requires a sterilization step such as boil sterilization or retort sterilization. The present invention relates to the field of packaging in which strong adhesion is required, such as water and detergents and bath additives.

[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 using a metal foil such as an aluminum foil as a gas barrier layer, which is less affected by temperature and humidity, has been generally used.

[0003] However, a packaging material using a metal foil such as an aluminum foil has an excellent gas barrier property, but the contents cannot be checked through the packaging material, and as a non-combustible material when discarded after use. There are drawbacks such as the necessity of processing and the inability to use a metal detector during the inspection.

[0004] Therefore, as a packaging material which overcomes these disadvantages, for example, inorganic oxides such as silicon oxide, aluminum oxide, magnesium oxide and the like described in US Pat. No. 3,442,686, JP-B-63-28017, etc. A film has been developed in which an object is formed on a polymer film by forming a vapor-deposited film by a forming means such as a vacuum vapor deposition method or a sputtering method. These deposited films are known to have transparency and gas barrier properties such as oxygen and water vapor,
It 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. Packaging materials that need to be combined with paper materials, especially when performing boil sterilization or retort sterilization, etc., flow to the market through various processes, so care must be taken when designing packaging. No.

[0006] Then, after the above-mentioned vapor-deposited film or the like was bonded to a sealant film and made into a bag, the contents such as water were filled and boil sterilization and retort sterilization were attempted.
It has been clarified that peeling occurs in a part of the seal portion after sterilization, resulting in poor appearance, and that the gas barrier property is deteriorated from the portion to deteriorate the content. In addition, the above-mentioned bag-making product was filled with a bathing agent as a content, and when the gas barrier properties and the laminating strength were compared before and after preservation after preservation for a certain period of time, peeling occurred after preservation or the laminating strength was reduced. There was also a problem that the gas barrier properties deteriorated from the part.

[0007] That is, the conditions used as a packaging material in such a case include transparency enough to allow the contents to be directly seen through, high gas barrier properties to block gases that affect the contents, and the like. It has high adhesiveness without loss of strength even after filling and storage, and has no gas barrier property deterioration even after boil sterilization or retort sterilization, and also has boil resistance and retort resistance such as no peeling phenomenon etc. There is a need, and at present no packaging material that meets all of these has been found.

[0008] Therefore, in the present invention, excellent transparency,
Provide a highly practical packaging material with high boil resistance and retort resistance that has high gas barrier properties and high adhesiveness, does not deteriorate in physical properties even after boil sterilization and retort sterilization, and does not cause peeling phenomenon. The purpose is to do.

[0009]

Means for Solving the Problems The present invention has been made to achieve the above-mentioned object, and the invention according to claim 1 provides an acrylic polyol, a polyester polyol and an isocyanate on at least one surface of a substrate made of a transparent plastic material. A strongly adhered gas barrier transparent laminate characterized by sequentially laminating a transparent primer layer composed of a compound and a compound with a silane coupling agent, and a vapor-deposited thin film layer composed of an inorganic oxide having a thickness of 5 to 300 nm.

According to a second aspect of the present invention, based on the first aspect, the silane coupling agent has an organic functional group which reacts with at least one of a hydroxyl group of an acrylic polyol and a polyester polyol or an isocyanate group of an isocyanate compound. This is a strongly adherent gas barrier transparent laminate.

According to a third aspect of the present invention, based on the second aspect, the organic functional group contained in the silane coupling agent is any one of an isocyanate group, an epoxy group, and an amino group. It is a strong adhesion gas barrier transparent laminate.

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

According to a fifth aspect of the present invention, based on the fourth aspect, the reaction catalyst is a tin compound.

According to a sixth aspect of the present invention, there is provided a strong adhesion gas barrier transparent laminate according to the fourth or fifth aspect, wherein the tin compound is any one of tin chloride, tin oxychloride and tin alkoxide. is there.

According to a seventh aspect of the present invention, based on the first to sixth aspects, the transparent primer layer has a thickness of 0.0
It is a strong adhesion gas barrier transparent laminate characterized by having a range of 1 to 2 μm.

According to an eighth aspect of the present invention, the inorganic oxide is aluminum oxide, silicon oxide, magnesium oxide or a mixture thereof based on the first to seventh aspects. Body.

According to a ninth aspect of the present invention, based on the first to eighth aspects, a gas barrier coating layer is further laminated on the transparent laminate of the present invention, wherein the gas barrier coating layer is formed of a water-soluble layer. A polymer and a coating agent mainly containing an aqueous solution or a water / alcohol mixed solution containing at least one of (a) one or more metal alkoxides and hydrolysates thereof, or (b) tin chloride, are applied and dried by heating. A strongly adhered gas barrier transparent laminate characterized by being a layer comprising:

A tenth aspect of the invention is based on the ninth aspect, wherein the metal alkoxide is tetraethoxysilane, triisopropoxyaluminum, or a mixture thereof. It is.

An eleventh aspect of the present invention is based on the invention of the ninth and tenth aspects, wherein the water-soluble polymer is a polyvinyl alcohol, wherein the water-soluble polymer is a polyvinyl alcohol.

[0020]

According to the present invention, a transparent primer layer having excellent dimensional stability and adhesion is provided on a transparent plastic substrate, and then an inorganic oxide layer having excellent gas barrier properties is laminated. Highly practical laminate for packaging without peeling or deterioration of gas barrier properties even after boil sterilization or retort sterilization, etc. Is obtained.

[0021]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in 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 composite of an acrylic polyol, a polyester polyol, an isocyanate compound, a silane coupling agent, etc., and a vapor-deposited thin film made of an inorganic oxide The layer 3 and the gas barrier coating layer 4 are sequentially laminated. in this case,
The gas barrier coating layer 4 may not be provided depending on required quality.

The substrate 1 is a transparent plastic material, and a transparent film is preferable in order to make use of the transparency of the vapor-deposited thin film layer. For example, polyethylene terephthalate (PET), 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 stretched or unstretched may be used, and 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, other layers may be laminated, the transparent primer layer 2, the inorganic oxide vapor-deposited thin film layer 3, the gas barrier Considering the workability when forming the functional coating layer 4, practically, in the range of 3 to 200 μm,
It is preferably 6 to 30 μm depending on the application.

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 occurrence of a peeling phenomenon after boil sterilization or retort sterilization, and to suppress a decrease in strength even when a content requiring strong adhesion is filled.

As a result of intensive studies, it is necessary that a composite of an acrylic polyol, a polyester polyol, an isocyanate compound, a silane coupling agent, and the like can be used as the transparent primer resin to achieve the above object.

The composite constituting the transparent primer layer will be described in more detail. Acrylic polyol is a polymer compound obtained by polymerizing an acrylic acid derivative monomer or a polymer compound obtained by copolymerizing an acrylic acid derivative monomer and other monomers, and having a hydroxyl group at a terminal. And the isocyanate group of 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 hydroxybutyl 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.
(KOH mg / g).

Polyester polyols include terephthalic acid, isophthalic acid, phthalic acid, methylphthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, succinic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, methyltetrahydroacid Acid raw materials such as phthalic acid, hexahydrophthalic acid and their reactive derivatives, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-hexanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexane At the inner end of a polyester resin obtained by a well-known manufacturing method from alcohol raw materials such as dimethanol, neopentyl glycol, bishydroxyethyl terephthalate, trimethylolmethane, trimethylolpropane, glycerin, and pentaerythritol. Those having more than five hydroxyl groups, are those which react with the isocyanate groups of the isocyanate compound added later.

The mixing ratio of the acrylic polyol and the polyester polyol is appropriately selected according to the required quality.
Generally, it is preferably in the range of 99/1 to 10/90 in terms of weight ratio. More preferably, 90/10 to 50
/ 50 range. A known method can be used for the mixing method, and is not particularly limited.

The isocyanate compound is added to increase the adhesion to a substrate or an inorganic oxide by a urethane bond formed by reacting with an acrylic polyol or a polyester polyol, and mainly acts as a crosslinking agent or a curing agent. I do. In order to achieve this, as an isocyanate compound, aromatic tolylene diisocyanate (TDI) or diphenylmethane diisocyanate (MD
I), aliphatic xylene diisocyanate (XDI)
And polymers and derivatives thereof such as monomer and hexadiene isocyanate (HMDI), and these are used alone or as a mixture.

The amount of the isocyanate compound to be added 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, causing a problem in processing. Therefore, the amount of the insocyanate compound added is such that the NCO group derived from the isocyanate compound is
It is preferably 50 times or less in terms of equivalent ratio with respect to the sum of the H group and the OH group derived from the polyester polyol, and particularly preferably when the NCO group and the OH group are blended in the same amount. A known method can be used for the mixing method, and is not particularly limited.

As the silane coupling agent, any silane coupling agent containing an organic functional group can be used. For example, ethyltrimethoxysilane, vinyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ- One or more silane coupling agents such as chloropropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, or a hydrolyzate thereof Can be used.

Further, among these silane coupling agents, those having a functional group which reacts with a hydroxyl group of a polyol or an isocyanate group of an isocyanate compound are particularly preferable. For example, those containing isocyanate groups such as γ-isocyanatopropyltriethoxysilane and γ-isocyanatopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β- (aminoethyl)- Those containing an amino group such as γ-aminopropyltriethoxysilane and γ-phenylaminopropyltrimethoxysilane, and further γ-glycidoxypropyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane And the like, and these may be used alone or in a mixture of two or more. In these silane coupling agents, an organic functional group present at one end shows an interaction in a composite comprising a polyol and an isocyanate compound, or a silane coupling agent containing a functional group which reacts with a hydroxyl group of a polyol or an isocyanate group of an isocyanate compound. A stronger primer layer is formed by giving a covalent bond by using a ring agent, and a silanol group generated by hydrolysis of an alkoxy group or the like at the other end is a metal in the inorganic oxide or a surface of the inorganic oxide. It exhibits high adhesion to inorganic oxides by strong interaction with a highly active hydroxyl group or the like, and can obtain desired physical properties. Therefore, a silane coupling agent obtained by a hydrolysis reaction with a metal alkoxide may be used. There is no problem even if the alkoxy group of the silane coupling agent is a chloro group, an acetoxy group or the like, and these alkoxy groups, a chloro group, an acetoxy group and the like are hydrolyzed to form a silanol group. It can be used in this composite.

The compounding ratio of the combination of the acrylic polyol and the polyester polyol to the silane coupling agent is preferably in the range of 1/1 to 1000/1 by weight, more preferably 2/1 to 100/100. 1 range. The dissolving and diluting solvent is not particularly limited as long as it can be dissolved and diluted, and examples thereof include ethyl acetate, esters such as butyl acetate, methanol, ethanol, alcohols such as isopropyl alcohol, ketones such as methyl ethyl ketone, Aromatic hydrocarbons such as toluene and xylene may be used alone or arbitrarily blended. However, since an aqueous solution such as hydrochloric acid or acetic acid may be used to hydrolyze the silane coupling agent, it is more preferable to use a solvent in which isopropyl alcohol or the like is arbitrarily mixed with ethyl acetate, which is a polar solvent, as a cosolvent. .

In addition, a reaction catalyst may be added for accelerating the reaction at the time of compounding the silane coupling agent. The catalyst to be added is a tin compound such as tin chloride (SnCl ₂ , SnCl ₄ ), tin oxychloride (SnOHCl, Sn (OH) ₂ Cl ₂ ), or tin alkoxide in view of reactivity and polymerization stability. Is preferred. These catalysts may be added directly at the time of compounding, or may be added by dissolving in a solvent such as methanol. If the addition amount is too small or too large, no catalytic effect can be obtained, so that the molar ratio is 1/10 to 1/1000 with respect to the silane coupling agent.
0 is preferable, and 1/100 to 1/1 is more preferable.
More preferably, it is in the range of 2,000.

As a method for preparing a primer solution for forming a composite film in the present invention, a composite solution is prepared by mixing an acrylic polyol, a polyester polyol, an isocyanate compound, and a silane coupling agent at an arbitrary mixing ratio. It is formed by coating it on the substrate 1. As a method of producing the composite solution, a silane coupling agent and an acrylic polyol, a polyester polyol are mixed, and a solvent and a diluent are added and diluted to an arbitrary concentration.
A method of preparing a composite solution by mixing with an isocyanate compound, or a method in which a silane coupling agent is previously mixed in a solvent, and then a mixture of an acrylic polyol and a polyester polyol is diluted with a solvent and a diluent to an arbitrary concentration. Then, there is a method of preparing a composite solution by adding an isocyanate compound.

Various additives such as tertiary amines, imidazole derivatives, metal salt compounds of carboxylic acids, quaternary ammonium salts, quaternary phosphonium salts and the like, and curing accelerators such as phenolic, sulfuric, and phosphating It is also possible to add an antioxidant such as a phytoid, a leveling agent, a flow regulator, a catalyst, a crosslinking reaction accelerator, a filler and the like.

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 0.001 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 coating, a knife edge coating, or a gravure coating is used to coat the substrate 1 and then the coating film is dried. The transparent primer layer 2 can be obtained by removing the solvent and curing the mixture.

The thin film layer 3 made of an inorganic oxide is made of a vapor-deposited film of an inorganic oxide such as aluminum oxide, silicon oxide, tin oxide, magnesium oxide, or a mixture thereof, and has transparency, oxygen, water vapor, etc. What is necessary is just to have the gas barrier property of the above. Among them, aluminum oxide and silicon 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 condition of the thickness of the thin film layer 3 varies 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. A 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 the vacuum evaporation apparatus by the vacuum evaporation method, an electron beam heating method, a resistance heating method, and an induction heating method are preferable, and in order to improve the adhesion between the thin film and the substrate and the denseness of the thin film, a plasma assist method or an ion It is also possible to use a beam assist method. Also,
At the time of vapor deposition, reactive vapor deposition such as blowing in oxygen gas may be used in order to increase the transparency of the deposited film.

The gas barrier coating layer 4 is provided on the inorganic oxide thin film layer 3 in order to provide gas barrier properties as high as aluminum foil depending on required quality.

The gas barrier coating layer 4 is made of an aqueous solution or a water / alcohol mixed solution containing at least one of a water-soluble polymer and (a) at least one metal alkoxide and a hydrolyzate or (b) tin chloride. It consists of a coating agent used as the main agent. A solution obtained by dissolving a water-soluble polymer and tin chloride in an aqueous (water or water / alcohol mixture) solvent, or a solution obtained by mixing a metal alkoxide directly or beforehand with a treatment such as hydrolysis is used for inorganic oxidation. It is formed by coating and heating and drying on the material thin film layer 3. Each component contained in the coating agent will be described in more detail.

The water-soluble polymer used for the coating agent in the present invention includes polyvinyl alcohol, polyvinylpyrrolidone, starch, methylcellulose, carboxymethylcellulose, sodium alginate and the like. In particular, when polyvinyl alcohol (hereinafter, referred to as PVA) is used as a coating agent for the laminate of the present invention, the gas barrier properties are most excellent. The PVA referred to here is generally obtained by saponifying polyvinyl acetate, and a few percent of acetic acid groups remain from so-called partially saponified PVA in which several tens of percent of acetic acid groups remain.
There is no particular limitation, including up to complete PVA that only remains.

Tin chloride is stannous chloride (SnCl ₂ ),
Stannic chloride (SnCl ₄ ) or a mixture thereof may be used, and either an anhydride or a hydrate can be used.

Further, the metal alkoxide is tetraethoxy.
Silane [Si (OC_TwoH_Five)_Four], Triisopropoxy
Aluminum [Al (O-2'-C_ThreeH₇)_Three]
General formula, M (OR)_n(M: Si, Ti, Al, Zr, etc.
Metal, R: CH_Three, C_TwoH _FiveSuch as an alkyl group)
Things. Among them, tetraethoxysilane, triiso
After propoxyaluminum is hydrolyzed,
Is relatively stable in this case.

Each of the above-mentioned components can be added to the coating agent alone or in a combination of several components. Further, as long as the gas barrier properties of the coating agent are not impaired, an isocyanate compound, a silane coupling agent, a dispersant, or a stabilizer is used. Known additives such as a viscosity modifier and a coloring agent can be added.

For example, an isocyanate compound added to a coating agent has two or more isocyanate groups (NCO groups) in its molecule. For example, tolylene diisocyanate (TDI), triphenylmethane triisocyanate (TTI) ), Tetramethylxylene diisocyanate (hereinafter, TMXDI), and polymers and derivatives thereof.

As a method of applying the coating agent, conventionally known means such as a commonly used dipping method, roll coating method, screen printing method, spray 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, other layers 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 provided to increase the breaking strength during sterilization of boiling and retort. In general, a biaxially stretched nylon film, a biaxially stretched polyethylene terephthalate film, It must be a type selected from biaxially oriented polypropylene films. The thickness is determined according to the material, required quality, and the like, but is generally in the range of 10 to 30 μm.
As a forming method, lamination can be performed by a known method such as a dry laminating method in which two adhesives such as a two-component curable urethane resin are used.

The heat seal layer is provided as an adhesive layer when forming a bag-like package. For example, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer and their metals A resin such as a crosslinked product is used. The thickness is determined according to the purpose, but is generally 15 to 200 μm.
Range. As a forming method, it is common to use a dry laminating method or the like in which a film-like material made of the above resin is bonded using an adhesive such as a two-component curable urethane resin, but all are laminated by a known method. be able to.

[0055]

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

<Preparation of Composite Solution> A) 9 parts by weight of acrylic polyol and 1 part by weight of polyester polyol were weighed in 2 parts by weight of 2- (epoxycyclohexyl) ethyltrimethylsilane (hereinafter abbreviated as EETMS) in a diluting solvent. Then, tin chloride (SnCl ₂ ) / methanol solution (0.003
mol / g) was 1/1 to EETMS.
Add to 35 mol and stir. Next, a mixed solution obtained by diluting a mixed solution obtained by adding triidyl isocyanate (hereinafter abbreviated as TDI) as an isocyanate compound to an OH group of an acrylic polyol and a polyester polyol so that an NCO group is equivalent to an OH group to an arbitrary concentration is obtained. A.

B) In a diluting solvent, 9 parts by weight of an acrylic polyol and 1 part by weight of a polyester polyol are weighed with respect to 1 part by weight of N-β- (aminoethyl) -γ-aminopropyltriethoxysilane and mixed and stirred. Next, a mixed solution obtained by adding TDI as an isocyanate compound so that the NCO group is equivalent to the OH group of the acrylic polyol and the polyester polyol at an arbitrary concentration is referred to as a composite solution B.

C) In a diluting solvent, 9 parts by weight of an acrylic polyol and 1 part by weight of a polyester polyol are weighed with respect to 1 part by weight of γ-isocyanatopropyltrimethylsilane and mixed and stirred. Next, a solution obtained by diluting a mixed solution obtained by adding TDI as an isocyanate compound so that NCO groups are equivalent to OH groups of acrylic polyol and polyester polyol to an arbitrary concentration is referred to as a composite solution C.

D) A composite solution D was prepared in the same manner except that 7 parts by weight of the acrylic polyol and 3 parts by weight of the polyester polyol were used in the composite solution A.

E) A composite solution E was prepared in the same manner except that 10 parts by weight of the polyester polyol was used in the composite solution A.

<Example 1> As the substrate 1, a thickness of 12 µm
The composite solution A as the transparent primer layer 2 was coated on one surface of the biaxially stretched PET film having a thickness of 0.1 by a gravure coating method.
1 μm was formed. Next, on the transparent primer layer 2, metal aluminum was evaporated by an electron beam heating type vacuum evaporation apparatus, oxygen gas was introduced therein, and aluminum oxide having a thickness of 20 nm was evaporated to form an inorganic oxide thin film layer 3. A transparent gas barrier transparent laminate of Example 1 was obtained.

<Example 2> On the inorganic oxide thin film layer 3 of Example 1, a coating agent having the following composition was further applied as a gas barrier coating layer 4 to a thickness of 0.5 μm by a gravure coating method.
Was formed to obtain a strongly adhered gas barrier transparent laminate of Example 2. The composition of the coating agent is determined by mixing the liquid with the liquid (w
(t%) in a 60/40 mixture. (Note: Tetraethoxysilane 10.4 g and hydrochloric acid (0.1N) 89.6 g
And stirred for 30 minutes to hydrolyze the solid content of 3 wt%
Hydrolysis solution (in terms of SiO ₂ ) 3 wt% water / isopropyl alcohol solution of polyvinyl alcohol (water:
90:10 by weight ratio of isopropyl alcohol))

Example 3 Example 2 was carried out in the same manner as in Example 2 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 method using a resistance heating method (not shown). Thus, a strongly adhered gas barrier transparent laminate of Example 3 was obtained.

Example 4 A strongly adhered gas barrier transparent laminate of Example 4 was obtained in the same manner as in Example 2, except that the composite solution B was used as the transparent primer layer 2.

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

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

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

Comparative Example 2 Example 2 was repeated except that the composite solution E was used as the transparent primer layer.
In the same manner as in the above, a transparent laminate of Comparative Example 2 was obtained.

<Dry Laminate 1> A biaxially stretched nylon film having a thickness of 15 μm as an intermediate layer was formed on the side of the inorganic oxide layer 3 or the gas barrier coating layer 4 of each of the examples and comparative examples produced as described above. Lamination was performed by a dry lamination method via a curable urethane-based adhesive, and an unstretched polypropylene film having a thickness of 70 μm was laminated as a heat seal layer by a dry lamination method via a two-liquid curable urethane-based adhesive.

<Dry Laminate 2> Similarly, a 50-μm-thick low-density polyethylene film as a heat-sealing layer is provided on the inorganic oxide layer 3 or the gas barrier coating layer 4 side of Examples and Comparative Examples in a two-component curable urethane. They were laminated by a dry lamination method via a system adhesive.

<Test 1> Four dry laminates of Examples and Comparative Examples were subjected to retort sterilization by 4
A seal pouch was prepared, filled with 150 g of water as a content, and subjected to retort sterilization at 125 ° C. for 30 minutes.
As an evaluation, the oxygen permeability before and after the retort (cc / m ² /
day), the laminate strength (gr / 15 mm), and the occurrence of the peeling phenomenon after retort was visually observed. Table 1 shows the results.

[0072]

[Table 1]

<Test 2> A four-sided seal pouch was prepared for each of the two dry laminates of Examples and Comparative Examples, and a powdered bath agent was filled as the content. Thereafter, the pouch is stored in an atmosphere of 40 ° C.-90% RH for one month, before and after storage, oxygen permeability (cc / m ² / day) and lamination strength (gr / 15 mm), and after storage by visual observation. The occurrence of the peeling phenomenon was observed. Table 2 shows the results.

[0074]

[Table 2]

In comparison with the embodiment, the comparative example was set under the conditions used as the above-mentioned packaging material, and was transparent enough to allow the contents to be directly seen through, and shielded from gases that affect the contents. High gas barrier properties, gas barrier properties do not deteriorate even after various sterilizations, sterilization resistance without generation of delamination, etc., does not satisfy all the strong adhesiveness whose strength has been degraded by the contents, but the examples satisfy all of them. It can be said that.

[0076]

As described above, according to the present invention, a versatile packaging material having excellent transparency and a high gas barrier property comparable to that of aluminum foil can be obtained. Because of its excellent adhesion, it can be widely used in the field of packaging.

[Brief description of the drawings]

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

[Explanation of symbols]

 1) transparent plastic substrate 2) transparent primer layer 3) inorganic oxide thin film layer 4) gas barrier coating layer

Continued on the front page F term (reference) 4F100 AA00C AA17C AA18C AA19C AA20C AB33C AH06D AH08D AK01A AK01D AK21D AK41A AK51B AS00B BA03 BA05 BA07 BA10A BA10C EH66C EJ38A EJ65BJJJBBJJBJJBJJBJJBJB11

Claims (11)

[Claims] 1. A transparent primer layer comprising a composite of an acrylic polyol, a polyester polyol, an isocyanate compound and a silane coupling agent on at least one surface of a substrate made of a transparent plastic material, having a thickness of 5 to 30.
A strongly adhered gas barrier transparent laminate, characterized by sequentially laminating a vapor-deposited thin film layer of 0 nm inorganic oxide. 2. The silane coupling agent according to claim 1, wherein said silane coupling agent has an organic functional group which reacts with at least one of a hydroxyl group of an acrylic polyol and a polyester polyol or an isocyanate group of an isocyanate compound.
The strongly adhered gas barrier transparent laminate according to the above. 3. The strongly laminated gas barrier transparent laminate according to claim 2, wherein the organic functional group contained in the silane coupling agent is any one of an isocyanate group, an epoxy group and an amino group. 4. The strongly adherent gas barrier transparent laminate according to claim 1, wherein a reaction catalyst is added to the composite. 5. The strongly adhered gas barrier transparent laminate according to claim 4, wherein the reaction catalyst is a tin compound. 6. The strongly adhered gas barrier transparent laminate according to claim 4, wherein said tin compound is any one of tin chloride, tin oxychloride and tin alkoxide. 7. The transparent primer layer having a thickness of 0.01
7. The thickness is in the range of .about.2 .mu.m.
The strongly adhered gas barrier transparent laminate according to the above. 8. The strongly adhered gas barrier transparent laminate according to claim 1, wherein said inorganic oxide is aluminum oxide, silicon oxide, magnesium oxide or a mixture thereof. 9. A structure in which a gas barrier coating layer is further laminated on the laminate according to claim 1, wherein said gas barrier coating layer comprises: a water-soluble polymer; and (a) one or more metal alkoxides. 2. A layer obtained by applying a coating agent mainly containing an aqueous solution or a water / alcohol mixed solution containing at least one of tin chloride and a hydrolyzate thereof or (b) tin chloride, and heating and drying the coating agent. 9. The strongly adhered gas barrier transparent laminate according to any one of items 1 to 8. 10. The strongly adherent gas barrier transparent laminate according to claim 9, wherein the metal alkoxide is tetraethoxysilane, triisopropoxyaluminum, or a mixture thereof. 11. The strongly adhered gas barrier transparent laminate according to claim 9, wherein the water-soluble polymer is polyvinyl alcohol.