JP2002058881A - Balloon formed of transparent evaporation film multilayer material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a balloon formed of a transparent evaporation film multilayer material with excellent gas barrier property free from the initiation of a crack and a pinhole when machined into a spherical bag as the balloon, without causing venting of gas such as hydrogen, helium or air filled in the balloon for a long time and having little environmental load when spent and discarded. SOLUTION: This balloon formed of the transparent evaporation film multiplayer material is characterized by using a laminated material with a heat sealed resin layer laminated, through an adhesive layer, on a transparent evaporation film with gas barrier property formed by successively laminating a primer layer and a deposited thin film layer comprising an inorganic oxide, in order on at least one side of a film base material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a balloon made of a multi-layered transparent vapor-deposited film having excellent gas barrier properties and improved gas sealing properties.

[0002]

2. Description of the Related Art Conventionally, balloons for toys, advertisements, etc. are made by heat-sealing a plastic film or natural or synthetic rubber to form a spherical bag filled with a gas such as hydrogen, helium, or air. Has been widely used. However, when natural or synthetic rubber is used, expansion and contraction occurs due to the ingress and egress of gas, and this gas barrier property deteriorates,
A few days later, there was a problem that gas escaped and withered.

[0003] When a plastic film is used, a material obtained by evaporating aluminum to improve gas barrier properties or a material obtained by coating a substrate having a low environmental load with polyvinyl alcohol (hereinafter referred to as PVA) is used. ing. As a plastic film, a polyamide film or a film made of ethylene vinyl alcohol is generally used in consideration of pinholes and heat sealing properties.

[0004] However, a plastic film on which aluminum is deposited is not preferable because it has a large environmental load at the time of disposal. In addition, a plastic film coated with PVA may have deteriorated gas barrier properties in a humid environment due to properties unique to PVA.

[0005] Although aluminum vapor-deposited films have high gas barrier properties, they tend to form pinholes and have low flexibility.
There is a high possibility that the gas barrier properties deteriorate. In order to solve this problem, there is known a method in which oxygen is introduced to deposit aluminum as aluminum oxide on the surface of a substrate when depositing aluminum.

The balloon is preferably made of a biaxially stretched polyamide film from the viewpoints of gas sealing workability and long-term gas pressure retention. However, when a barrier film is formed by forming a vapor-deposited layer of an inorganic compound, the film has a low hygroscopic property. Therefore, there is a problem that the adhesion strength with the vapor deposition layer is reduced with time, and thus it has not been put to practical use.

Therefore, as means for improving the adhesion strength between the vapor deposition layer and the plastic film substrate, the vapor deposition surface of the film substrate is generally subjected to corona discharge treatment and plasma treatment. Even if a proper surface treatment is performed, there is a problem that the adhesion strength of the vapor deposition layer is reduced due to the influence of moisture, and the vapor deposition layer floats when peeled between layers or when bent. Further, as a means for improving the adhesion strength between the vapor-deposited layer and the plastic film substrate, it is common practice to perform an anchor coating treatment on the surface of the film substrate, but for example, a two-part curable urethane-based anchor coating agent is used. Even when the anchor coat layer is provided, similarly, the adhesion strength of the deposited layer is reduced due to the influence of moisture,
There has been a problem that the vapor deposition layer floats when peeled between layers or when bent.

Further, polyethylene terephthalate (hereinafter referred to as PET) is used as a film base of the vapor-deposited film.
Is generally used. Although it has an advantage that a vapor deposition layer can be stably laminated, it has not been put to practical use because of its inferior flexibility, piercing strength and toughness as compared with the above-mentioned polyamide film.

Therefore, there has been a demand for a gas barrier material which does not generate cracks and pinholes when the balloon is processed into a spherical bag and does not allow gas filled in the balloon to escape for a long time.

[0010]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and has no cracks or pinholes when processed into a spherical bag as a balloon.
Provide a balloon made of a multi-layered transparent vapor-deposited film that has excellent gas barrier properties and does not cause gas to escape over a long period of time when a gas such as helium or air is charged into the balloon, has excellent gas barrier properties, and has a low environmental impact when used and disposed. The purpose is to:

[0011]

Means for Solving the Problems The present invention has been made to solve the above problems, and the invention of claim 1 is to provide a film thin film layer comprising a primer layer and an inorganic oxide on at least one side of a film substrate in order. A balloon comprising a transparent vapor-deposited film multi-layered material, wherein a laminate obtained by laminating a heat-sealing resin layer on a laminated transparent vapor-deposited film having a gas barrier property via an adhesive layer is used.

According to a second aspect of the present invention, a gas barrier coating layer is further laminated on the vapor-deposited thin film layer made of the inorganic oxide according to the first aspect, and a heat barrier is formed on the coating layer via an adhesive layer. A balloon comprising a transparent vapor-deposited film multi-layered material using a laminate in which a sealing resin layer is laminated.

According to a third aspect of the present invention, there is provided a balloon comprising the multilayered transparent vapor-deposited film according to the first or second aspect, wherein the film substrate is made of a polyamide film.

According to a fourth aspect of the present invention, there is provided any one of the first to third aspects.
Or a multilayer comprising a transparent vapor-deposited film multilayer according to claim 1.
In the above method, the primer layer has a general formula RSi (OR
1) _Three(R is a substituted / unsubstituted alkyl group, vinyl group, etc.
And R1 represents an alkyl group).
Trifunctional organosilane or its hydrolyzate
Compounds with ril polyols and isocyanate compounds
It is characterized by consisting of.

According to a fifth aspect of the present invention, the trifunctional organosilane according to the fourth aspect is characterized in that R is a trifunctional organosilane.
(R: an alkyl group, a vinyl group, a glycidoxypropyl group, etc.) containing an epoxy group or an isocyanate group.

According to a sixth aspect of the present invention, in the composite of the fourth aspect, the general formula M (OR2) n (M is a metal element, R2 is an alkyl group such as CH ₃ or C ₂ H ₅₎ To n
Is a balloon formed of a transparent vapor-deposited film multilayer, characterized by adding a metal alkoxide represented by the following formula (1) or a hydrolyzate of the metal alkoxide.

According to a seventh aspect of the present invention, the metal in the metal alkoxide or the hydrolyzate of the metal alkoxide according to the sixth aspect is Si, Al, Ti, Zr or a mixture thereof. It is a balloon made of a multi-layered film.

According to an eighth aspect of the present invention, there is provided a balloon comprising a transparent vapor-deposited film multilayer according to any one of the first to seventh aspects, wherein a reaction catalyst is added to the composite of the primer layer. Features.

A ninth aspect of the present invention is a balloon comprising a transparent vapor-deposited film multilayer, wherein the reaction catalyst according to the eighth aspect is a tin compound.

According to a tenth aspect of the present invention, the tin compound according to the ninth aspect is a tin compound selected from tin chloride, tin oxychloride and tin alkoxide. It is a balloon that becomes.

The eleventh aspect of the present invention is characterized in that the thickness of the primer layer formed of the multilayered transparent vapor-deposited film according to the first to tenth aspects is in the range of 0.01 to 2 μm.

According to a twelfth aspect of the present invention, there is provided a balloon comprising the multilayered transparent vapor-deposited film according to the first to eleventh aspects,
The inorganic oxide is aluminum oxide or silicon oxide,
Alternatively, it is a mixture thereof.

According to a thirteenth aspect of the present invention, in the balloon comprising the transparent vapor-deposited film multilayered product according to any one of the first to twelfth aspects, the heat-sealable resin layer is a polyolefin-based resin layer. And

According to a fourteenth aspect of the present invention, the gas barrier coating layer according to the second aspect is characterized in that the water-soluble polymer and at least one of (a) one or more metal alkoxides and a hydrolyzate thereof, and (b) tin chloride. A balloon comprising a transparent vapor-deposited film multilayer, which is obtained by applying a coating agent mainly comprising an aqueous solution or a mixed solution of water / alcohol, and drying the coating agent.

According to a fifteenth aspect of the present invention, there is provided a balloon comprising a transparent vapor-deposited film multilayer, wherein the metal alkoxide according to the fourteenth aspect is tetraethoxysilane, triisopropoxyaluminum, or a mixture thereof. .

[0026] According to a sixteenth aspect of the present invention, there is provided a balloon comprising a transparent vapor-deposited film multilayer, wherein the water-soluble polymer contained in the gas barrier coating layer according to the fourteenth aspect is polyvinyl alcohol.

<Function> According to the present invention, a primer layer for increasing the adhesion strength to a vapor-deposited layer, an inorganic oxide vapor-deposited layer having excellent gas barrier properties, and a coating layer are formed on a polyamide film substrate resistant to external impact. Excellent gas barrier properties and deterioration of gas barrier properties due to the use of a laminate in which a polyolefin resin with high hot tack properties, high sealing properties during heat sealing, and high bag breaking strength is used. Thus, a balloon made of a transparent vapor-deposited film with low practical use and high disposal properties is obtained.

[0028]

Embodiments of the present invention will be described below in detail with reference to the drawings. FIG. 1 is an explanatory view for explaining a balloon formed of the transparent vapor-deposited film multilayer of the present invention. FIG. 1A schematically shows a balloon formed of the transparent vapor-deposited film multilayer of the present invention. It is sectional drawing. FIG. 1B is an enlarged cross-sectional view of a transparent vapor-deposited film multilayer as an example of the balloon of the present invention.

As shown in FIG. 1 (b), a transparent vapor-deposited film multilayer material constituting a balloon is, for example, a primer layer 1b and an inorganic oxide thin film layer formed by vapor-depositing an inorganic oxide on a substrate 1a. 1c and a coating layer 1d are sequentially laminated, an adhesive layer 2 is further provided, and a heat seal layer 3 is laminated.

The substrate 1a in the present invention is a film made of a polyamide resin having excellent flexibility among plastic materials, and is preferably transparent if the transparency of the vapor-deposited thin film layer is utilized. For example, well-known polyamide resins such as 6-nylon obtained by a ring-opening polymerization reaction of ε-caprolactam and 6,6-nylon obtained by a polycondensation reaction of hexamethylenediamine with an adipate can be used. Those processed into a film shape are used. In particular, those stretched arbitrarily in the biaxial direction are preferable because of excellent mechanical strength and dimensional stability. Further, on the surface of the substrate, various well-known additives and stabilizers, for example, an antistatic agent, an ultraviolet ray inhibitor, a plasticizer, a lubricant, and the like may be used to improve the adhesion to the thin film. Further, a corona treatment, a low-temperature plasma treatment, and an ion bombardment treatment can be performed as a pretreatment. Further, chemical treatment, solvent treatment, or the like may be performed.

The thickness of the substrate 1a is not particularly limited, but the other layers, such as the primer layer 1b, the inorganic oxide vapor-deposited thin film layer 1c, the gas barrier coating layer 1d, and other layers are laminated. In consideration of workability in the case of lamination, it is generally in the range of 5 to 100 μm, and practically 10 to 30 μm.
The range of m is preferred.

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

The primer layer 1b according to the present invention is provided on a base material 1a made of a polyamide resin, improves the adhesion between the base material 1a and the inorganic oxide thin film layer 1c made of an inorganic oxide, and reduces the delamination. It is intended to prevent generation and deterioration of gas barrier properties. As a result of intensive studies, it is necessary that a composite of a trifunctional organosilane or a hydrolyzate thereof, an acrylic polyol and an isocyanate compound can be used as a primer layer to achieve the above object.

The trifunctional organosilane has the general formula RS
It is a compound represented by i (OR1) ₃ (R: substituted or unsubstituted alkyl group, vinyl group, etc., R1: alkyl group).
At this time, the substituent of R preferably contains an epoxy group or an isocyanate group. For example, ethyltrimethoxysilane, vinyltrimethoxysilane, glycidoxypropyltrimethoxysilane containing an epoxy group in R, glycidoxytrimethoxysilane, epoxycyclohexylethyltrimethoxysilane, or R ′ containing an isocyanate group Γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane and the like. These compounds may be used alone or as a mixture of two or more.

Further, the trifunctional organosilane used in the present invention may be a hydrolyzate of the above compound or the like. At this time, the substituent of R ′ preferably contains an epoxy group or an isocyanate group. As a method for obtaining a hydrolyzate, a known method such as a method of directly adding a luminous alkali or the like to a trifunctional organosilane to perform hydrolysis can be used.

The 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 another monomer, and having a hydroxyl group at a terminal. And reacts with an isocyanate group of an isocyanate compound to be added later. Among them, ethyl methacrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate,
A polymer obtained by polymerizing an acrylic acid derivative monomer such as hydroxybutyl methacrylate alone, or an acrylic polyol obtained by adding and copolymerizing another monomer such as styrene is preferably used. In consideration of the reactivity with the isocyanate compound, the hydroxyl value is 5 to 200 (KO).
Hmg / g).

Further, the isocyanate compound is added to increase the adhesion to the substrate 1a or the inorganic oxide layer 1c by urethane bonds formed by reacting with the acrylic polyol, and is mainly used as a crosslinking agent or a curing agent. Act as To achieve this, an aromatic tolylene diisocyanate (TDI) is used as an isocyanate compound.
And diphenylmethane diisocyanate (MDI), aliphatic xylene diisocyanate (XDI), hexadiisocyanate (HMDI), and monomers such as isophorone diisocyanate (IPDI), and polymers and derivatives thereof. These may be used alone or Used as a mixture.

The mixing ratio of the acrylic polyol and the isocyanate compound used for the primer layer 1b is not particularly limited. However, if the amount of the isocyanate compound is too small, the curing may be poor. There is a problem. Therefore, the blending ratio of the acrylic polyol and the isocyanate compound is determined by the isocyanate group (NCO group) derived from the isocyanate compound.
Is preferably 50 times or less the OH group derived from the acrylic polyol, particularly preferably when the NCO group and the OH group are blended in an equal amount. A well-known method can be used as the mixing method, and is not particularly limited.

Further, at the time of preparing the composite, a metal alkoxide or a hydrolyzate thereof may be added to improve the liquid stability. This metal alkoxide is represented by a general formula M (O) such as tetraethoxysilane [Si (OC ₂ H ₅ ) ₄ ], tripropoxy aluminum [Al (OC ₃ H ₇ ) ₃ ].
R) n (M: metal element, n: oxidation number of metal) or a hydrolyzate thereof. Among them, tetraethoxysilane, tripropoxyaluminum or a compound of both are preferable because they are relatively stable in an aqueous solvent.

Further, a reaction catalyst is added to the composite of the primer layer. As the reaction catalyst, a tin compound such as tin chloride, tin oxychloride, or tin alkoxide is used. In addition to the catalyst, the primer further includes various additives such as curing accelerators such as tertiary amines, imidazole derivatives, metal salt compounds of carboxylic acids, quaternary ammonium salts, and quaternary phosphonium salts; It is also possible to add an antioxidant such as a sulfur type or a phosphite type, a leveling agent, a flow regulator, a crosslinking reaction accelerator, a filler, and the like.

As a method for forming the primer layer 1b, 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, knife edge coat or gravure coat is used. be able to.

The thickness of the primer layer 1b 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. If the thickness is less than 0.01 μm, it is difficult to obtain a uniform coating, and the adhesion may be reduced. If the thickness exceeds 2 μm, the flexibility of the coating cannot be maintained. It is not preferable because cracks may occur. 0.
It is particularly preferred that it is in the range of 0.5 to 0.5 μm.

The deposited layer 1c made of an inorganic oxide in the present invention is made of a deposited film of an inorganic oxide such as aluminum oxide, silicon oxide or a mixture thereof, and has transparency and a gas barrier property against oxygen, water vapor and the like. What is necessary is just to have.

There are various methods for forming the vapor-deposited layer 1c made of an inorganic oxide on the primer layer 1b, which can be formed by a normal vacuum vapor-deposition method. , A plasma vapor deposition (CVD) method, or the like. 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. 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 heating method is used. It is also possible to use a beam assist method. In addition, in order to increase the transparency of the deposited film, reactive deposition may be performed by blowing oxygen gas or the like during the deposition.

The optimum condition of the thickness of the vapor deposition layer 1c varies depending on the kind and constitution of the inorganic compound to be used. If the thickness is less than 5 nm, a uniform film may not be obtained, or the film thickness may not be sufficient, and may not function as a gas barrier material. On the other hand, if the thickness exceeds 100 nm, the flexibility of the thin film cannot be maintained, and the thin film may be cracked by external factors such as bending and stretching after the film is formed. There is a problem. More preferably, 10
５０50 nm.

The coating layer 1d in the present invention is provided on the inorganic oxide vapor-deposited layer 1c in order to provide a gas barrier property as high as a metal foil made of a metal such as aluminum.

The coating layer 1d is composed of a water-soluble polymer and (a)
One or more metal alkoxides and hydrolysates, or
And (b) a coating agent mainly composed of an aqueous solution containing at least one of tin chloride and a water / alcohol mixed solution. A water-soluble polymer and tin chloride are converted to an aqueous system (water or water /
A mixture obtained by coating a solution obtained by dissolving with a solvent) or a solution obtained by directly or preliminarily hydrolyzing a metal alkoxide on the inorganic oxide thin film layer 1c and drying by heating. .

The water-soluble polymer used for the coating agent 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, the gas barrier properties are most excellent. The PVA referred to here is generally obtained by saponifying polyvinyl acetate, and includes a range from so-called partially saponified PVA in which acetic acid groups remain to several tens% to complete PVA in which only a few% of acetic acid groups remain. ,
There is no particular limitation.

As a method for applying the coating, conventionally known means such as a commonly used dipping method, roll coating method, screen printing method, spraying method and the like can be used. It is sufficient that the thickness of the coating is not less than 0.01 μm. However, if the thickness is not less than 50 μm, cracks are easily generated in the coating.

Further, another layer can be laminated on the coating layer 1d. For example, a printing layer and a heat sealing layer. The printing layer is formed for practical use as a packaging bag or the like, and various pigments are added to conventionally used ink binder resins such as urethane, acrylic, nitrocellulose, rubber, and vinyl chloride. This is a layer composed of an ink to which additives such as an extender pigment, a plasticizer, a desiccant, a stabilizer and the like are added, and a character, a picture, and the like 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 0.1-2.0 μm.

The polyolefin resin layer 3 is provided as a sealing layer when forming a bag-like package or the like, and is made of a heat-sealing polyolefin resin. By laminating a polyolefin resin layer having excellent hot-tack property and sealing property at the time of heat sealing and strong bag breaking strength as a package, a package having high transparency and gas barrier properties can be obtained. Given the above properties, linear low-density polyethylene is preferred. The thickness of the film is suitably from 2 to 100 μm, preferably from 3 to 60 μm. As a forming method, it is common to use a dry lamination method in which a film made of the above resin is bonded using an adhesive such as a two-component curable urethane resin, but any of them can be laminated by a known method. .

Then, the laminated body obtained as described above is heat-sealed to form a bag-shaped balloon.

In the present invention, printing, attachment of an advertisement message, etc. to a substrate comprising a transparent vapor-deposited film multilayer can be arbitrarily performed according to the purpose.

[0054]

The present invention will be described below with reference to specific examples of a balloon made of a transparent vapor-deposited film multilayered product according to the present invention.

Example 1 15 μm thick substrate 1a
On one side of a biaxially stretched polyamide film (Ny) as a primer layer 1b, in a diluting solvent (ethyl acetate), as an acrylic polyol and an isocyanate compound, TDI
Was diluted to an arbitrary concentration with a mixed solution obtained by adding the NCO group to the OH group of the acrylic polyol so as to have an equivalent amount, and a thickness of 0.1 μm was formed by a gravure coating method. Next, metal aluminum was evaporated on the primer layer 1b by a vacuum evaporation apparatus using an electron beam heating method, oxygen gas was introduced therein, and aluminum oxide having a thickness of 25 nm was evaporated to form an inorganic oxide thin film layer 1c. Further, a coating layer 1d having a thickness of 0.5 μm was formed on the coating layer by a gravure coating method using the coating agent shown below, and a laminated film was formed. As the polyolefin-based resin layer 3, linear low-density polyethylene was used, and a dry-lamination was performed to obtain a transparent vapor-deposited film multilayered product A in which a heat seal layer having a thickness of 60 μm was laminated. The obtained transparent vapor-deposited film multilayered product A was evaluated based on the evaluation method shown below, and the results are shown in Table 1.

[Coating agent] A coating agent obtained by mixing a liquid and a liquid in the following mixing ratio. Liquid: a hydrolyzed solution having a solid content of 3% by weight (in terms of SiO 2) obtained by adding 89.6 g of 0.1N hydrochloric acid to 10.4 g of tetraethoxysilane and stirring for 30 minutes to hydrolyze. 60% by weight liquid: water / isopropyl alcohol solution. (Water: isopropyl alcohol = 90: 10 mixed by weight ratio) 40% by weight

[Evaluation Method] Hydrogen Permeability: Hydrogen permeability from the sealant surface to the front direction under the conditions of 30 ° C.-Free and pressure of 2 atm using a gas permeability measuring device manufactured by Yanaco Analytical Industry Co., Ltd. Was measured.・ Water vapor permeability: 40 ° C-90% by MOCON method
The water vapor permeability was measured under the condition of RH. -Laminate strength: T-type peeling, peeling speed 300mm /
Under the condition of min, the peel strength was measured and expressed as a laminate strength. -Puncture strength: Puncture strength was measured according to JIS Z1707.・ Disposability: A configuration with a small environmental load at the time of disposal is indicated by a circle.
Further, many configurations having a large environmental load are indicated by crosses. As a comprehensive evaluation, a three-level evaluation was performed: excellent (represented by a mark), slightly poor (represented by a mark), and poor (represented by a cross).

<Embodiment 2> In Embodiment 1, the thickness 25
A transparent vapor-deposited film multilayer B was obtained in the same manner as in Example 1 except that silicon oxide having a thickness of nm was deposited and the inorganic oxide thin film layer 1c was laminated. The obtained transparent vapor-deposited film multilayer B was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 1 In Example 1, the inorganic oxide thin film layer 1c and the coating layer 1 were provided without providing the primer layer 1b.
Except having laminated | stacked d, it carried out similarly to Example 1, and obtained the transparent vapor deposition film multilayer product C. The obtained transparent vapor-deposited film multilayer C was evaluated in the same manner as in Example 1, and the results were shown in Table 1.
It was shown to.

<Comparative Example 2> In Example 1, except that the primer layer 1b and the coating layer 1d were not provided and the inorganic oxide thin film layer 1c was formed, metal aluminum was vapor-deposited instead of aluminum oxide. A transparent vapor-deposited film multilayer product D was obtained in the same manner as in Example 1. The obtained transparent vapor-deposited film multilayer D was evaluated in the same manner as in Example 1,
The results are shown in Table 1.

<Comparative Example 3> A synthetic resin film in which aluminum terephthalate (PET) was laminated with 9 μm of aluminum foil on 12 μm of polyethylene terephthalate (PET) was used. Thus, a multilayer product E obtained by laminating a heat seal layer having a thickness of 60 μm was obtained. The obtained multilayer product E was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

<Comparative Example 4> In Example 1, the base material 1a
A laminate F was obtained in the same manner as in Example 1 except that a polyethylene terephthalate (PET) film was used instead of the biaxially stretched polyamide film. The obtained multilayer product F was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

<Comparative Example 5> In Example 1, the primer layer 1b and the coating layer 1 were provided without providing the inorganic oxide thin film layer 1c.
d in the same manner as in Example 1 except that
I got The obtained multilayer product F was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

<Comparative Example 6> In Example 1, the base material 1a
Using a polyethylene terephthalate (PET) film instead of a biaxially stretched polyamide film, without providing an inorganic oxide thin film layer 1c, a primer layer 1b and a coating layer 1d.
Were laminated in the same manner as in Example 1 except that was laminated. The obtained multilayer product H was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

[0065]

[Table 1]

Next, a balloon was prepared using the multilayers obtained in Example 1 and Comparative Examples 4 to 6, and the presence or absence of outgassing, the separation between the substrate and the vapor deposited layer, the printability and flexibility. Was evaluated. The printability and flexibility were evaluated on a three-point scale: excellent (represented by a mark), slightly poor (represented by a mark), and poor (represented by a cross). Table 2 shows the results.
Shown in

[0067]

[Table 2]

From Tables 1 and 2, it can be seen that the properties of the transparent vapor-deposited film multilayered product of the present invention obtained in Examples 1 and 2 and the balloon produced using the same are excellent in a comprehensive judgment. confirmed.

[0069]

As described above, according to the present invention,
Because it is a balloon formed using a transparent vapor-deposited film multilayer material, when processing into a spherical bag as a balloon, there was no generation of cracks and pinholes, and gas such as hydrogen, helium, air was filled in the balloon. It has become possible to provide a balloon made of a transparent vapor-deposited film multilayered product that does not cause gas to escape for a long time, has excellent gas barrier properties, and has a low environmental load when used and discarded. The balloon made of the transparent vapor-deposited film multilayered product of the present invention is preferably used for toys, advertisements, and the like by printing or advertising messages on the substrate of the transparent vapor-deposited film multilayered material as required.

[Brief description of the drawings]

FIG. 1A is a cross-sectional view schematically showing a balloon made of a transparent vapor-deposited film multilayer of the present invention. (B)
1 is an enlarged cross-sectional view of a transparent vapor-deposited film multilayer as an example of a balloon according to the present invention.

[Explanation of symbols]

 1a Base material 1b Primer layer 1c Inorganic oxide thin film layer 1d Coating layer 2 Adhesive layer 3 Polyolefin resin layer 4 Balloon body

Continued on the front page F-term (reference) 2C150 DD09 DD13 DE02 EB02 FB32 FB43 FB55 4F100 AA05D AA17B AA19B AA20B AH06G AH08D AH08G AK01A AK01C AK03C AK21D AK46A AK51G AK52J01B02A04B01A01B01A01B12A01B01A02A

Claims (16)

[Claims] 1. A heat-sealing resin layer is laminated via an adhesive layer to a transparent vapor-deposited film having a gas barrier property in which a primer layer and a vapor-deposited thin film layer composed of an inorganic oxide are sequentially laminated on at least one side of a film substrate. A balloon comprising a multilayer of a transparent vapor-deposited film, characterized by using a laminate. 2. A gas barrier coating layer is further laminated on the vapor-deposited thin film layer comprising the inorganic oxide according to claim 1, and a heat seal resin layer is laminated on the coating layer via an adhesive layer. A balloon comprising a transparent vapor-deposited film multi-layered product using the laminated product. 3. The balloon according to claim 1, wherein the film substrate is made of a polyamide film. 4. The method according to claim 1, wherein the primer layer has a general formula RSi (OR
1) ₃ (R is a substituted or unsubstituted alkyl group, vinyl group, etc., R1 is an alkyl group), a trifunctional organosilane or a hydrolyzate thereof, and an acrylic polyol and an isocyanate compound. The balloon comprising the multilayered transparent vapor-deposited film according to any one of claims 1 to 3, wherein the balloon comprises a composite of: 5. The trifunctional organosilane according to claim 4, wherein
R constituting the trifunctional organosilane (R: alkyl group,
A balloon comprising a transparent vapor-deposited film multilayer, wherein an epoxy group or an isocyanate group is contained in a vinyl group, a glycidoxypropyl group, or the like. 6. The compound of claim 4, wherein the compound of the general formula M (OR2) n (M is a metal element and R2 is CH
₃ , a metal alkoxide represented by an alkyl group such as C ₂ H ₅ , and n represents an oxidation number of a metal element) or a hydrolyzate of the metal alkoxide. Become a balloon. 7. The method according to claim 6, wherein the metal in the metal alkoxide or the hydrolyzate of the metal alkoxide is S
A balloon comprising a transparent vapor-deposited film multilayer, which is i, Al, Ti, Zr or a mixture thereof. 8. A balloon comprising a multilayered transparent vapor-deposited film according to claim 1, wherein a reaction catalyst is added to the composite of the primer layer. 9. A balloon comprising a transparent vapor-deposited film multilayer, wherein the reaction catalyst according to claim 8 is a tin compound. 10. A balloon comprising a transparent vapor-deposited film multilayer, wherein the tin compound according to claim 9 is any tin compound selected from tin chloride, tin oxychloride and tin alkoxide. 11. The primer layer having a thickness of 0.01 to 0.01.
The balloon comprising the transparent vapor-deposited film multilayer according to claim 1, wherein the balloon has a thickness of 2 μm. 12. The balloon according to claim 1, wherein the inorganic oxide is aluminum oxide, silicon oxide, or a mixture thereof. 13. The heat-sealable resin layer is a polyolefin-based resin layer.
A balloon comprising the transparent vapor-deposited film multilayer according to any one of the above. 14. The gas barrier coating layer according to claim 2, wherein the gas barrier coating layer comprises an aqueous solution or water containing a water-soluble polymer and at least one of (a) at least one metal alkoxide and a hydrolyzate thereof, and (b) tin chloride. A balloon comprising a transparent vapor-deposited film multilayer, which is obtained by applying a coating agent containing a / alcohol mixed solution as a main component and drying the coating agent. 15. A balloon comprising a transparent vapor-deposited film multilayer, wherein the metal alkoxide according to claim 14 is tetraethoxysilane, triisopropoxyaluminum, or a mixture thereof. 16. A balloon comprising a transparent vapor-deposited film multilayer, wherein the water-soluble polymer contained in the gas barrier coating layer according to claim 14 is polyvinyl alcohol.