JPH10264292A - Transparent laminated body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To impart an easy adhesiveness to a plastic film, and also impart a content protective property simultaneously by laminating in order on a transparent plastic base material a transparent primer layer consisting of a mixture of an acrylic resin and isocyanate resin and a thin film layer consisting of an inorganic compound. SOLUTION: The base material 1 is a film consisting of transparent plastic having a transparent primer layer 2 and a thin film layer 3 consisting of an inorganic compound laminated by the turn. For the plastic base material 1, there is preferably used each biaxially oriented polyethylene terephthalate film and polypropylene film. The transparent primer layer 2 is made up of a mixture of acrylic resin and isocyanate resin, wherein acrylic polyol is preferable for acrylic resin, and tolylendiisocyanate is preferable for isocyanate resin. For inorganic compound to be used for the thin film 3, aluminum oxide is preferable, which is formed by a vacuum evaporation method or the like.

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 foods, medicines and the like.

[0002]

2. Description of the Related Art In the field of packaging materials, laminates such as sealant films having heat sealing properties are known.
As a method of laminating these, a method of laminating via an adhesive, a method of laminating via a hot-melted resin layer, and an extrusion (hereinafter abbreviated as EXT) laminating are generally used. Since the stronger the adhesive strength, the better,
The base film and the sealant film are often subjected to an easy adhesion treatment. Easy adhesion treatment method is chemical surface treatment,
Although there is a method such as gas flame treatment, corona treatment is generally used for controllability and uniformity of treatment.

In the case of extruding a non-polar resin such as polyethylene in EXT lamination, even if the substrate is corona-treated, the adhesive strength is insufficient, so that an organic titanium-based, polyethylene imine-based, or isocyanate-based anchor coating agent is applied before lamination. In some cases.

[0004] In any of the methods, at present, the laminate strength frequently deteriorates with the lapse of time due to the contents to be filled. In particular, with the aim of imparting gas and water vapor barrier properties to the packaging material, aluminum oxide,
When a thin film layer made of an inorganic compound such as magnesium oxide, tin oxide, or silicon oxide is laminated, the adhesiveness between the plastic film surface and the thin film layer made of the inorganic compound is weak, and the thin film layer often peels off.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and provides easy adhesion to a substrate or a plastic film of a sealant. It is an object of the present invention to provide a transparent laminated body which also has so-called content resistance, in which the laminate strength is not deteriorated even when the laminated body strength is lowered. In particular, the present invention aims to further improve the oxygen permeability barrier property.

[0006]

Means for Solving the Problems The present invention has been made to achieve this object, and the invention of claim 1 provides a transparent primer layer comprising a mixture of an acrylic resin and an isocyanate resin on a transparent plastic substrate, A transparent laminated body, characterized by sequentially laminating thin film layers made of an inorganic compound.

A second aspect of the present invention is a transparent laminate according to the first aspect, wherein the acrylic resin is an acrylic polyol.

According to a third aspect of the present invention, based on the first and second aspects, the mixing ratio of the acrylic polyol resin and the isocyanate resin used in the transparent primer layer is such that the NCO group derived from the isocyanate resin is an acrylic polyol resin. It is a transparent laminate characterized by being 50 times or less the OH group derived therefrom.

According to a fourth aspect of the present invention, based on the first to third aspects, the thickness of the transparent primer layer is set to 0.1.
It is a transparent laminated body having a range of 001 to 2 μm.

According to a fifth aspect of the present invention, based on the first to fourth aspects, the thin film layer made of the inorganic compound is made of aluminum oxide, magnesium oxide, tin oxide, silicon oxide, or a mixture thereof. It is a transparent laminate characterized.

According to a sixth aspect of the present invention, there is provided the transparent laminate according to the first to fifth aspects, wherein the transparent plastic substrate is a polyester film.

According to a seventh aspect of the present invention, there is provided a transparent laminate according to the first to fifth aspects, wherein the transparent plastic substrate is a stretched polypropylene film.

[0013] According to an eighth aspect of the present invention, in the configuration in which a gas barrier coating layer is further laminated on the transparent laminate according to the first to seventh aspects, the gas barrier coating comprises an aqueous polymer;
A coating agent mainly comprising an aqueous solution or a water / alcohol mixed solution containing at least one of (a) one or more metal alkoxides and hydrolysates thereof, and (b) tin chloride, is applied and heated and dried. It is a transparent laminated body characterized by these.

According to a ninth aspect of the present invention, there is provided a transparent laminate according to the first to eighth aspects, wherein the water-soluble polymer is polyvinyl alcohol.

The invention according to claim 10 is the invention according to claims 1 to 9
The transparent laminate according to the invention described above, wherein the metal alkoxide is tetraethoxysilane or triisopropoxyaluminum, or a mixture thereof.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail with reference to the drawings. FIG. 1 is a sectional view of the transparent laminate of the present invention.

The laminate of FIG. 1 will be described. The substrate 1 in FIG. 1 is a film made of a transparent plastic, on which a transparent primer layer 2 and a thin film layer 3 made of an inorganic compound are laminated.

The plastic substrate 1 used in the present invention is a material used as a usual packaging material such as polyolefin, polyester, polyamide, polyvinyl chloride, polyimide, etc., or a copolymer of these polymers. Although not performed, a biaxially stretched polyethylene terephthalate film, a polypropylene film, or the like is preferably used in view of transparency, thermal stability, and the like.

If the substrate or the primer layer of the present invention is transparent, the effect is more prominent. However, even if it is not completely transparent, it is also effective if it is translucent, colored transparent, or opaque.

The thickness of the plastic film is 3 to 2
In the range of 00 μm, a thickness of 6 to 100 μm is desirable.
In addition, there is no problem in including additives and stabilizers (antistatic agent, ultraviolet absorber, plasticizer, lubricant, etc.). Further, there is no problem even if the film is subjected to surface treatment (corona treatment, plasma treatment, etc.).

The transparent primer layer 2 according to the present invention is provided on a plastic base material, and enhances the adhesiveness when providing a barrier thin film layer made of an inorganic compound, when providing a printing layer, or when laminating, and Another object of the present invention is to prevent the deterioration of the lamination strength over time after filling the contents.

The acrylic resin used as a primer is a general resin produced by a radical polymerization reaction from an acrylic acid ester or a methacrylic acid ester under the action of ultraviolet light, a polymerization initiator, or a polymerization catalyst. Solution polymerization, suspension polymerization, and emulsion polymerization can be used.

Acrylic esters and methacrylic esters as monomers include n-alkyl acrylates such as methyl ester and ethyl ester, isopropyl acrylate, isobutyl acrylate, t-butyl acrylate, cyclohexyl acrylate, β-hydroxyethyl acrylate, β-hydroxy Propyl acrylate, glycidyl acrylate, ethylene glycol diacrylate, diethylaminoethyl acrylate, 2-
Cyanoethyl acrylate, β-ethoxyethyl acrylate, aryl acrylate, alkoxycarbonyl acrylate, benzyl acrylate, sulfo acrylate, acrylate containing phosphorus or halogen, fluoroalkyl acrylate, benzoyloxyalkyl acrylate, tetrahydrofurfuryl acrylate, trimethylolpropane triacrylate, There is no particular limitation on 1,4-butanediol diacrylate and the like, and the type and the mixing ratio can be freely determined depending on the required physical properties.

The other monomer component may be a copolymer with styrene, vinyl acetate, vinylidene chloride, vinyl chloride, butadiene, ethylene, vinyl ether, N-methylolacrylamide, acrolein, or the like. The mixing ratio can be freely determined depending on the required physical properties.

Further, a resin obtained by introducing a functional group having reactivity with another functional group such as a hydroxyl group, a carboxyl group, or an epoxy group into these acrylic resins may be used. For example, those having hydroxyl groups introduced at both terminals and acrylic polyols having introduced a monomer such as β-hydroxyethyl methacrylate. Considering the reactivity with the isocyanate resin which is another component of the transparent primer layer 2 according to the present invention, it is desirable to use an acrylic polyol having a hydroxyl value of 5 to 200.

The isocyanate-based resin added to the primer mainly acts as a crosslinking agent.

As the isocyanate resin, aromatic tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), aliphatic hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), xylylene diisocyanate ( XDI) and the like, and are not particularly limited. Among them, TDI-based compounds are preferable.

Additives other than those described above, such as tertiary amines, imidazole derivatives, metal salt compounds of carboxylic acids, quaternary ammonium salts, quaternary boronium salts, and other curing accelerators; It is also possible to add an antioxidant such as a sulfur-based or phosphite-based agent, a leveling agent, a flow regulator, a catalyst, a crosslinking reaction accelerator, a filler, and the like.

A known method can be used for mixing the acrylic resin and the isocyanate resin, and there is no particular limitation.

The mixing ratio of the acrylic resin and the isocyanate resin is not particularly limited, but if the amount of the isocyanate resin is too small, the curing of the primer layer may be insufficient. Since a film may not be obtained, the compounding ratio of the acrylic resin and the isocyanate resin is preferably such that the NCO groups derived from the isocyanate resin are not more than 50 times the OH groups derived from the acrylic polyol. Particularly preferred is the case where NCO group / OH group = 1/1. In addition, the dissolution of the primer resin is possible by a usual method and is not particularly limited.

The thickness of the primer layer is not limited.
When the thickness is less than 01 μm, the coating amount is not stable and the adhesive effect may be weakened. On the other hand, when the thickness is more than 2 μm, the flexibility of the film is lost and cracks are easily formed.
μm is desirable. As a method for forming the primer layer, a known method can be used. Also, the drying method is not particularly limited, and a normal method can be used.

The thin film layer 3 made of an inorganic compound according to the present invention is provided for the purpose of improving the barrier properties of the substrate, and includes, for example, oxides such as Al, Si, Sn, Mg, etc.
It is formed from a simple substance such as nitride or fluoride, or a mixture. Among them, aluminum oxide, magnesium oxide, tin oxide, silicon oxide, and mixtures thereof are particularly excellent in gas barrier properties. However, the inorganic compound thin film layer of the present invention is not limited to the above compounds, and any material that meets the above conditions can be used.

Although the thickness of the inorganic compound layer varies depending on the application and the thickness of the base plastic film, there is a problem that it is difficult to control the thickness uniformly below 5 nm. If the thickness is 300 nm or more, cracks are likely to occur, and the kneading property is reduced.

The inorganic compound layer can be formed by a usual method such as a dry coating method. For example, a vacuum deposition method, a sputtering method, an ion plating method, or the like can be used. However, in consideration of productivity, vacuum evaporation is currently the best. 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 can be used.

It is also possible to laminate another base material (such as plastic film or paper) or a heat-sealing resin on the laminate of the present invention. Well-known methods (dry lamination, EXT lamination, etc.) can be used for the lamination method, and there is no particular limitation.

A printing layer can be provided on the inorganic compound layer of the laminate of the present invention. Ink used for the printing layer is generally a mixture of a binder resin such as urethane, acrylic, nitrocellulose, rubber, and vinyl chloride mixed with a pigment, a plasticizer, a desiccant, and a stabilizer. .
The present invention is not particularly limited to inks. The printing method includes an offset method, a gravure method, and a silk screen method, and is not particularly limited.

Another embodiment of the present invention will be described in detail with reference to the drawings. FIG. 2 is a sectional view of the laminate of the present invention.

The laminate of FIG. 2 will be described. The substrate 1 in FIG. 2 is a film made of a transparent plastic, in which a transparent primer layer 2, a thin film layer 3 made of an inorganic compound, and a gas barrier coating 4 are sequentially laminated.

The plastic substrate 1, the primer layer 2, and the thin film layer 3 made of an inorganic compound used in the present invention can be the same as those described above.

The gas barrier coating 4 is provided on the thin film layer 3 made of an inorganic compound, and is provided to provide a gas barrier property as high as that of an aluminum foil. (B) tin chloride, or an aqueous solution or a water / alcohol mixed solution containing at least one of tin chloride (b). A solution prepared by dissolving a water-soluble polymer and tin chloride in an aqueous (water or water / alcohol mixture) solvent, or a solution prepared by mixing a metal alkoxide directly or in advance with a treatment such as hydrolysis is used. It is formed by coating and heating and drying the thin film layer 3 made of a compound. 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, polyvinyl pyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, sodium alginate and the like. In particular, when polyvinyl alcohol (hereinafter referred to as PVA) is used for the coating agent of 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. The so-called partially saponified PVA in which acetic acid groups remain several tens%, the acetic acid groups are several%
There is no particular limitation, including the complete PVA that only remains.

In addition, tin chloride is stannous chloride (SnCl _2).
), Stannic chloride (SnC ₄ ), or a mixture thereof, and either an anhydride or a hydrate can be used.

Further, the metal alkoxide is tetraethoxy.
Sisilane [Si (OC_Two H_Five )_Four ], Triisopropoxy
Aluminum [Al (O-2'-C_Three H₇ )_Three ]Such
The general formula of M (OR) n (M: Si, TI, Al, Zr
Metals such as R: CH_Three , C _Two H_Five Alkyl groups such as
It is represented by Above all, tetraethoxysila
And triisopropoxy aluminum are hydrolyzed,
It is preferable because it is relatively stable even in a system solvent.

Each of the above-mentioned components can be added to the coating agent alone or in combination of several components. Further, as long as the barrier properties of the coating agent are not impaired, isocyanate compounds, silane coupling agents, dispersants, and stabilizers , A viscosity modifier, a coloring agent, and the like.

For example, an isocyanate compound to be added to a coating agent has two or more isocyanate groups (NCO) in its molecule. For example, monomers such as tolylene diisocyanate, triphenylmethane isocyanate, and tetramethylxylene diisocyanate And their polymers and derivatives.

As a method of applying the coating agent, a commonly used method such as a dipping method, a roll coating method, a screen printing method and a spray printing method is used. Although the thickness of the coating varies depending on the type of the coating agent, the thickness after drying may be in the range of 0.01 to 100 μm. It is desirable that the thickness be 50 μm.

Another substrate (plastic film, paper, etc.) may be laminated on the laminate of the present invention, or a resin having heat sealing properties may be laminated. Well-known methods (dry lamination, EXT lamination, etc.) can be used for the lamination method, and there is no particular limitation.

A printing layer may be provided on the barrier coating layer of the laminate of the present invention. The ink used for the printing layer is urethane, acrylic, nitrocellulose, rubber,
A mixture of a binder resin such as a vinyl chloride resin and a pigment, a plasticizer, a desiccant, and a stabilizer is generally used.
The present invention is not particularly limited to inks. The printing method includes an offset method, a gravure method, and a silk screen method, and is not particularly limited.

The laminate of the present invention is provided with a primer layer composed of a mixture of an acrylic resin and an isocyanate resin on a transparent plastic substrate to form a barrier thin film layer composed of an inorganic compound, an ink, a film or a resin layer to be laminated. Can be improved, and furthermore, deterioration of the laminate strength over time when the contents are filled can be prevented.

[0050]

EXAMPLES The laminate of the present invention will be described in more detail with reference to Examples.

<Mixing of primers> Primers were mixed in the following mixing ratio. The acrylic polyol resin used as a primer in this experiment is Dianal LR209 manufactured by Mitsubishi Rayon Co., Ltd. As an isocyanate resin, Coronate L manufactured by Nippon Polyurethane Industry Co., Ltd. is used.
Was used. Primer A: Acrylic polyol resin and isocyanate resin were mixed such that (OH group of acrylic polyol resin) :( NCO group of isocyanate resin) was 1: 1. Primer B: Acrylic polyol resin and isocyanate resin were mixed such that (OH group of acrylic polyol resin) :( NCO group of isocyanate resin) was 1: 2. Primer C: Acrylic polyol resin and isocyanate resin were mixed such that (OH group of acrylic polyol resin) :( NCO group of isocyanate resin) was 1: 4. The above resin mixture is treated with ethyl acetate as a diluting solvent for NV
(Solid content) was diluted to 5%.

Example 1 Primer A was laminated on one side of a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm (in this experiment, Lumirror P60 manufactured by Toray Industries, Inc.) to a thickness of 0.10 μm by coating. .

Example 2 A primer B was laminated to a thickness of 0.10 μm on one side of a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm (in this experiment, Lumirror P60 manufactured by Toray Industries, Inc.). .

Example 3 A primer C was laminated on one surface of a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm (Lumirror P60 manufactured by Toray Industries, Ltd. in this experiment) to a thickness of 0.10 μm. .

Comparative Example 1 An untreated biaxially stretched polyethylene terephthalate film having a thickness of 12 μm (Lumilar P60 manufactured by Toray Industries, Inc. was used in this experiment).

Comparative Example 2 A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm (Lumirror P60 manufactured by Toray Industries, Inc. was used in this experiment) was coated with only an acrylic polyol resin to a thickness of 0.10 μm on one surface. Laminated.

Comparative Example 3 A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm (Lumirror P60 manufactured by Toray Industries, Inc. was used in this experiment) was coated with an acrylic polyol resin and an isocyanate resin (OH of the acrylic polyol resin). Group): (NCO of isocyanate resin)
Base) is 1:64.
It was laminated by coating with a thickness of m.

On the primer layers of the laminates of Examples 1 to 3 and Comparative Examples 1 to 3, a gas barrier thin film layer composed of an inorganic compound was laminated, and further a gas barrier coating was laminated.
Finally, a heat-sealing resin was laminated by a dry lamination method. However, without laminating the gas barrier coating,
A device in which a heat-sealing resin was directly laminated on a thin film layer made of an inorganic compound was also manufactured.

<Lamination of Thin Film Layer Made of Inorganic Compound> Vacuum deposition was performed by an electron beam heating method to laminate a thin film layer made of silicon oxide or aluminum oxide. When silicon oxide is laminated, the thickness is set to 400 to 500 °,
When aluminum oxide is laminated, 100 to 30
The layers were laminated so as to have a thickness of 0 °.

<Lamination of Gas Barrier Coating> A coating agent having the following composition was laminated to a thickness of 0.3 μm. (Coating composition) A Hydrochloric acid (0.1%) was added to 10.4 g of tetraethoxysilane.
N) 89.6 g of a hydrolyzed solution having a solid content of 3 wt% (in terms of SiO) hydrolyzed by stirring for 30 minutes. B A 3 wt% water / isopropyl alcohol solution of polyvinyl alcohol (90:10 by weight ratio of water: isopropyl alcohol) A solution obtained by mixing Solution A and Solution B at a mixing ratio (wt%) of 60/40.

<Dry Lamination> An unstretched polyethylene film having a thickness of 50 μm was laminated via a urethane-based adhesive layer. In this experiment, UBOB manufactured by Tamapoli Corporation was used as the unstretched polyethylene film.

<Test 1> The lamination strength of the laminated body having a silicon oxide layer as a thin film layer composed of an inorganic oxide of Examples 1, 2, and 3 and Comparative Examples 1, 2, and 3 laminated as described above was set to ten tens of mils. Measured. The peeled portion is a primer layer and a silicon oxide layer, a silicon oxide layer, or an adhesive layer. The sample is a 15 mm wide strip. 180 with the substrate straightened
° Measured by peeling. Measurement conditions are crosshead speed 3
00mm / min, chart speed 100mm / mi
n.

<Test 2> Four-side sealing using a laminate having a silicon oxide layer as a thin film layer made of an inorganic oxide of Examples 1, 2, and 3 and Comparative Examples 1, 2, and 3 laminated as described above. Is prepared, filled with about 25 g of toothpaste as a content, and stored under an atmosphere of 40 ° C.-90% RH for 3 months.
The change in laminate strength over time was measured. The measurement conditions are
Test 1 was the same as above.

<Test 3> The lamination strength of the laminate having an aluminum oxide layer as a thin film layer composed of an inorganic oxide of Examples 1, 2, and 3 and Comparative Examples 1, 2, and 3 laminated as described above was set to ten tens of mils. Measured. The peeled part is a primer layer and an aluminum oxide layer, an aluminum oxide layer, or an adhesive layer. The sample is a 15 mm wide strip. The measurements were taken at 180 ° peel with the substrate straightened. The measurement conditions were a crosshead speed of 300 mm / min and a chart speed of 100 mm / min.

<Test 4> Using a laminate having an aluminum oxide layer as a thin film layer made of an inorganic oxide in Examples 1, 2, and 3 and Comparative Examples 1, 2, and 3 laminated as described above,
Make a side seal pouch, and add about 2 toothpaste as contents.
5 g was filled and stored for 3 months in an atmosphere of 40 ° C.-90% RH, and the change in lamination strength was measured over time. The measurement conditions were the same as in Test 3 above.

<Test 5> The oxygen barrier properties of the laminates having a silicon oxide layer as a thin film layer composed of an inorganic oxide of Examples 1, 2, and 3 and Comparative Examples 1, 2, and 3 laminated as described above were determined to be M.
It was measured by OCON OXTRAN (manufactured by Modern Control). The measurement conditions were 25 ° C.-100% RH.

<Test 6> A test was conducted using a laminate having a silicon oxide layer as a thin film layer composed of an inorganic oxide in each of Examples 1, 2, 3, and 4 and Comparative Examples 1, 2, and 3 laminated as described above. Make a side seal pouch, and about 25g of toothpaste as contents
It was filled and stored in an atmosphere of 40 ° C.-90% RH for 3 months, and the change in oxygen barrier properties was measured over time. The measurement conditions were the same as in Test 5 above.

<Test 7> The oxygen barrier properties of the laminates having an aluminum oxide layer as a thin film layer made of an inorganic oxide of Examples 1, 2, and 3 and Comparative Examples 1, 2, and 3 laminated as described above were evaluated by MOCONOXTRAN. (Modern Control). The measurement conditions were 25 ° C.-100% RH.

<Test 8> Using a laminate having an aluminum oxide layer as a thin film layer composed of an inorganic oxide in Examples 1, 2, and 3 and Comparative Examples 1, 2, and 3 laminated as described above,
Make a side seal pouch, and add about 2 toothpaste as contents.
5 g was filled, stored for 3 months in an atmosphere of 40 ° C. and 90% RH, and the change in oxygen barrier property was measured over time. The measurement conditions were the same as in Test 7 above.

<Test Results> Test results are summarized in Tables 1 and 2. Table 1 shows the measurement results of the lamination strength (g / 15 mm), and Table 2 shows the oxygen permeability (cc / m 2 · da).
It is a measurement result of y). From the results of Tests 1 and 3, it can be seen that the lamination strength was improved by providing the primer layer. Furthermore, the results of Tests 2 and 4 show that the present invention was also compared with those of Comparative Example 1 having no primer layer and those of Comparative Examples 2 and 3 containing no isocyanate resin or containing too much isocyanate resin. It can be seen that the film provided with the primer layer has excellent adhesiveness and excellent content resistance.

Although the results of Tests 5 and 7 did not show any remarkable improvement in the oxygen barrier properties particularly with respect to oxygen due to the provision of the primer layer, as shown in the results of Tests 6 and 8, The effect of suppressing the deterioration of the barrier property over time during the storage of the contents is provided. In addition, it can be seen that a configuration in which a barrier coating is laminated on a thin film layer made of an inorganic compound exhibits better barrier properties.

[0072]

[Table 1]

[0073]

[Table 2]

The laminate of the present invention will be described in further detail using another embodiment.

Example 4 A 20 μm-thick biaxially stretched polypropylene film (Pyrene P2102 manufactured by Toyobo Co., Ltd. was used in this experiment) was coated with a primer A to a thickness of 0.10 μm on one surface. .

Example 5 A primer B having a thickness of 0.10 μm was laminated on one surface of a biaxially stretched polypropylene film having a thickness of 20 μm (Pyrene P2102 manufactured by Toyobo Co., Ltd. in this experiment). .

Example 6 A primer C was laminated to a thickness of 0.10 μm on one side of a biaxially oriented polypropylene film having a thickness of 20 μm (Pyrene P2102 manufactured by Toyobo Co., Ltd. in this experiment). .

Comparative Example 4 Biaxially stretched polypropylene film having a thickness of 20 μm, Pyrene P21 manufactured by Toyobo Co., Ltd.
02 unprocessed product.

Comparative Example 5 A biaxially oriented polypropylene film having a thickness of 20 μm, in which a resin layer was laminated on the surface by coextrusion in order to enhance the adhesiveness. In this experiment, MB110 manufactured by Mimura Nimura Co., Ltd. was used.

On the primer layers of the laminates of Examples 4 to 6 and Comparative Examples 4 and 5, a gas barrier thin film layer composed of an inorganic compound was laminated, and a gas barrier coating was further laminated.
Finally, a heat-sealing resin was laminated by a dry lamination method. However, without laminating the gas barrier coating,
A device in which a heat-sealing resin was directly laminated on a thin film layer made of an inorganic compound was also manufactured.

<Lamination of Thin Film Layer Made of Inorganic Compound> Vacuum evaporation was performed by an electron beam heating method to laminate a thin film layer made of silicon oxide or aluminum oxide. When silicon oxide is laminated, the thickness is set to 400 to 500 °,
When aluminum oxide is laminated, 100 to 30
The layers were laminated so as to have a thickness of 0 °.

<Lamination of Gas Barrier Coating> A coating agent having the following composition was laminated to a thickness of 0.3 μm. (Coating composition) A Hydrochloric acid (0.1%) was added to 10.4 g of tetraethoxysilane.
N) 89.6 g of a hydrolyzed solution having a solid content of 3 wt% (in terms of SiO) hydrolyzed by stirring for 30 minutes. B A 3 wt% water / isopropyl alcohol solution of polyvinyl alcohol (90:10 by weight ratio of water: isopropyl alcohol) A solution obtained by mixing Solution A and Solution B at a mixing ratio (wt%) of 60/40.

<Dry Lamination> An unstretched polypropylene film having a thickness of 30 μm was laminated via a urethane-based adhesive layer. In this experiment, Unilux RS503C manufactured by Idemitsu Petrochemical Co., Ltd. was used.

<Test 9> The lamination strength of a laminate having a silicon oxide layer as a thin film layer composed of an inorganic oxide of Examples 4, 5, 6 and Comparative Examples 4, 5 laminated as described above was measured by Tensilon. did. The peeled part is the base material and the primer layer,
It is a silicon oxide layer or an adhesive layer. The sample is 15m
Strip width of m width. The measurements were taken at 180 ° peel with the substrate straightened. The measurement conditions were a crosshead speed of 300 mm /
min, chart speed 100 mm / min.

<Test 10> A laminate having a silicon oxide layer as a thin film layer composed of an inorganic oxide of Examples 4, 5, 6 and Comparative Examples 4, 5 laminated as described above was subjected to 40 ° C.-90% RH.
Was stored for one month in an atmosphere of the above, and the change in laminate strength was measured over time. The measurement conditions were the same as in Test 9 above.

<Test 11> The lamination strength of a laminate having an aluminum oxide layer as a thin film layer made of an inorganic oxide of Examples 4, 5, 6 and Comparative Examples 4, 5 laminated as described above was measured by tensilon. did. The peeled part is the base material and the primer layer, the aluminum oxide layer, or the adhesive layer. The sample is a 15 mm wide strip. The measurements were taken at 180 ° peel with the substrate straightened. Measurement conditions: crosshead speed 300 mm / min, chart speed 100 m
m / min.

<Test 12> A laminate having a silicon oxide layer as a thin film layer composed of an inorganic oxide of each of Examples 4, 5, and 6 and Comparative Examples 4 and 5 laminated at 40 ° C. and 90% RH was prepared.
Was stored for one month in an atmosphere of the above, and the change in laminate strength was measured over time. The measurement conditions were the same as in Test 11 above.

<Test 13> The oxygen barrier properties of the laminates having silicon oxide layers as the thin film layers made of the inorganic oxides of Examples 4, 5, and 6 and Comparative Examples 4, 5 which were laminated as described above were measured.
It was measured by CON OXTRAN (manufactured by Modern Control). The measurement conditions were 25 ° C.-100% RH.

<Test 14> A laminate having a silicon oxide layer as a thin film layer composed of an inorganic oxide of Examples 4, 5 and 6 and Comparative Examples 4 and 5 laminated at 40 ° C.-90% RH
Was stored for one month in an atmosphere of the above, and the change in laminate strength was measured over time. The measurement conditions were the same as in Test 13 above.

<Test 15> The oxygen barrier properties of the laminates having an aluminum oxide layer as a thin film layer composed of an inorganic oxide of Examples 4, 5, and 6 and Comparative Examples 4, 5 laminated as described above were evaluated using MOCON OXTRAN ( Modern Control Co.). The measurement conditions were 25 ° C.-100% RH.

<Test 16> A four-side sealed pouch using a laminate having an aluminum oxide layer as the thin film layer composed of the inorganic oxide of Examples 4, 5, 6 and Comparative Examples 4, 5 laminated as described above. And add about 25 toothpaste as contents
g, and stored in an atmosphere of 40 ° C.-90% RH for one month, and a change in oxygen barrier property with time was measured. The measurement conditions were the same as in Test 7 above.

<Test Results> The test results are summarized in Tables 3 and 4. Table 3 shows the measurement results of the lamination strength (g / 15 mm), and Table 4 shows the oxygen permeability (cc / m ² · da).
It is a measurement result of y).

[0093]

[Table 3]

[0094]

[Table 4]

From the results of Tests 9 and 11, it can be seen that by providing the primer layer, the lamination strength can be improved as in the case of Comparative Example 5 having an adhesive resin layer. Further, it can be seen from the results of Tests 10 and 12 that little deterioration in moisture resistance is observed.

Further, from the results of Tests 13 and 15, it can be seen that the barrier properties are greatly improved. In general, the surface of a polypropylene substrate or adhesive resin layer is weak to heat, and the heat during vapor deposition may make the formation of a thin film layer made of inorganic oxide unstable, but the surface of the acrylic polyol resin layer It is considered that the formation of the base material stabilizes the surface of the base material against heat during vapor deposition and has an effect of uniformly forming a thin film layer made of an inorganic oxide.

[0097]

As described above, according to the present invention, it is possible to obtain a versatile packaging material which is excellent in adhesiveness when laminating and excellent in adhesiveness over time when filling contents. In particular, when laminating a thin film layer made of an inorganic compound for the purpose of imparting a barrier property centering on oxygen to a packaging material, a plastic having low adhesion and a barrier thin film layer (a thin film layer made of an inorganic compound) are used. A packaging material having excellent adhesion and barrier properties can be obtained.

[0098]

[Brief description of the drawings]

FIG. 1 is a sectional view of the present invention.

FIG. 2 is a cross-sectional view of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Plastic base material 2 Transparent primer layer 3 Thin film layer made of inorganic compound 4 Barrier coating layer

──────────────────────────────────────────────────続 き Continued on front page (51) Int.Cl. ⁶ Identification code FI B32B 27/36 B32B 27/36 27/40 27/40 B65D 65/40 B65D 65/40 D

Claims (10)

[Claims] 1. A transparent laminate, comprising: a transparent primer layer composed of a mixture of an acrylic resin and an isocyanate resin; and a thin film layer composed of an inorganic compound sequentially laminated on a substrate composed of a transparent plastic. 2. The transparent laminate according to claim 1, wherein said acrylic resin is an acrylic polyol. 3. The compounding ratio of the acrylic polyol resin and the isocyanate resin used in the transparent primer layer is such that the NCO groups derived from the isocyanate resin are not more than 50 times the OH groups derived from the acrylic polyol resin. 3. The transparent laminate according to 1 or 2. 4. The thickness of the transparent primer layer is 0.001.
4. The method according to claim 1, wherein the distance is in a range of from about 2 μm to about 2 μm.
The transparent laminate according to the above. 5. The transparent laminate according to claim 1, wherein the thin film layer made of the inorganic compound is aluminum oxide, magnesium oxide, tin oxide, silicon oxide, or a mixture thereof. 6. The transparent laminate according to claim 1, wherein said transparent plastic substrate is a polyester film. 7. The transparent laminate according to claim 1, wherein the transparent plastic substrate is a stretched polypropylene film. 8. A structure in which a gas barrier coating layer is further laminated on the transparent laminate according to claim 1, wherein the gas barrier coating comprises an aqueous polymer, (a) one or more metal alkoxides and A transparent laminate, which is a layer obtained by applying a coating agent mainly containing an aqueous solution or a water / alcohol mixed solution containing at least one of the hydrolyzate and (b) tin chloride, and drying by heating. . 9. The transparent laminate according to claim 1, wherein said water-soluble polymer is polyvinyl alcohol. 10. The transparent laminate according to claim 1, wherein the metal alkoxide is tetraethoxysilane, triisopropoxyaluminum, or a mixture thereof.