JPH0434590A - Balloon - Google Patents

Abstract

PURPOSE:To improve pinhole resistance and printability by forming a gas barrier type resin layer of biaxially stretched and laminated films laminated with a polyamide layer, an ethylene/vinyl acetate copolymer hydrolyzate layer and a polyamide layer in this order. CONSTITUTION:The biaxially stretched and laminated films which are laminated with the polyamide layer having 3 to 10mu thickness, the ethylene/vinyl acetate copolymer hydrolyzate later having 3 to 20mu thickness and the polyamide layer of 3 to 10mu thickness in this arranging order and has 10 to 30mu total thickness. The balloon which has an excellent form holding ability and a floating holding ability in combination and has high pinhole resistance is obtd. if the biaxially stretched and laminated films have the thickness within this range. In addition, the balloon has an excellent gas barrier property, strength and form holding ability. The pinhole resistance and printability are improved in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a balloon, and more particularly, to a balloon that has excellent floating retention ability and shape retention ability, and improved pinhole resistance and printability. It is something.

[Conventional technology]

Various membrane materials have been known for balloons, but recently, biaxially oriented polyvinyl alcohol resin layers or metal vapor deposition layers have been developed for balloons with excellent floating and shape retention capabilities. A balloon comprising a composite film of a gas barrier resin layer including a biaxially oriented polyvinyl alcohol resin layer and a heat sealing resin layer has been proposed (Japanese Patent Laid-Open No. 2-43036).

[Invention or problem to be solved]

However, the above-mentioned balloon has a problem that pinhole resistance is poor and pinholes are likely to occur during transportation before the balloon is inflated. In addition, particularly in decoration applications, printing is often performed on the film surface of balloons, but polyvinyl alcohol-based resins have a problem in that they have poor printability and cannot be finished neatly.

An object of the present invention is to provide a balloon that has excellent floating retention ability and shape retention ability, and has improved pinhole resistance and printability.

[Means to solve the problem]

The above object of the present invention is to consist of a composite film of a gas barrier resin layer (A) with a thickness of 10 to 30 μm and a heat sealable resin layer (B) with a thickness of 3 to 30 μm. ) is a biaxially stretched laminated film in which a polyamide layer with a thickness of 3 to 10μ, a saponified ethylene-vinyl acetate copolymer layer with a thickness of 3 to 20μ, and a polyamide layer with a thickness of 3 to 10μ are laminated in the listed order. This is achieved by using a balloon that

The present invention will be explained in detail below.

The balloon of the present invention, like conventional balloons, is made of a composite film of a gas barrier resin layer (A) and a heat sealable resin layer (B).

First, the gas barrier resin layer (A) will be explained.

In the present invention, the gas barrier resin layer (A) includes a polyamide layer with a thickness of 3 to 10 μm, a saponified ethylene-vinyl acetate copolymer layer with a thickness of 3 to 20 μm, and a saponified ethylene-vinyl acetate copolymer layer with a thickness of 3 to 10 μm.
polyamide layers laminated in the listed order, total thickness 10~
A 30μ biaxially stretched laminated film is used.

The polyamide resin used in the polyamide layer used in the present invention includes - for boat fishing, nylon 6, nylon 66, nylon 12, nylon 6/66, aromatic nylon, etc.
Specifically, the raw materials include ε-caprolactam, enantlactam, capryllactam, lauryllactam,
Lactams such as α-pyrrolidone, α-piperidone,
Nylon salts of ω-amino acids or dicarboxylic acids and diamines such as 6-aminocaproic acid, 7-aminononanoic acid, 9-aminononanoic acid, and 11-aminoundecanoic acid are used.

Specific examples of dicarboxylic acids include malonic acid, succines, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, and tetradecanedioic acid. , hexadecanedionic acid, hexadenedionic acid, octadecanedionic acid, octadenedionic acid,
Eicosadionic acid, eicosenedionic acid, tocosadionic acid, 2. 2. Aliphatic dicarboxylic acids such as 4-trimethyladipic acid, 1. Dibasic acids such as alicyclic dicarboxylic acids such as 4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, aromatic dicarboxylic acids such as xylylene dicarboxylic acid,
Specific examples of diamines include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, Tridecamethylene diamine, hexadecamethylene diamine, octadecamethylene diamine, 2. 2. 4 (or 2. 4. 4) -
Examples include aliphatic diamines such as trimethylhexamethylene diamine, cyclohexane diamine, methylcyclohexane diamine, alicyclic diamines such as bis-(4,4'aminocyclohexyl)methane, and aromatic diamines such as xylylene diamine. .

The polyamide resin described above may contain well-known additives such as various stabilizers, fillers, pigments, dyes, lubricants, antiblocking agents, and various thermoplastic resins, as long as they do not exceed the spirit of the present invention. .

The saponified ethylene-vinyl acetate copolymer (EVOH) used in the present invention is produced by saponifying an ethylene-vinyl acetate copolymer, and has an ethylene content of 20 to 20%.
70 mo1%, preferably 25 to 50 mo1%, saponification degree of vinyl acetate component is 95 mo1% or more, preferably 9
8 mo1% or more is usually used. When the ethylene content is less than 20 mo1%, melt extrudability is insufficient and discoloration is likely to occur, while when it exceeds 70 mo1%, physical properties such as oxygen barrier properties and printability are insufficient. Moreover, when the degree of saponification is less than 95 mo1%, oxygen barrier properties and moisture resistance are insufficient.

The above EVOH contains a small amount of propylene, isobutyne, α
- α- such as octene, α-dodecene, α-octadecene, etc.
It may contain comonomer components such as olefins, unsaturated carboxylic acids, salts thereof, partial alkyl esters, complete alkyl esters, nitriles, amides or anhydrides, or unsaturated sulfonic acids or salts thereof. Also,
There is no problem even if a small amount of polyolefin resin, polyester resin, polyamide resin, etc. is mixed with EVOH.

The gas barrier resin layer (A) used in the present invention is a biaxially stretched laminate film of polyamide/saponified ethylene vinyl acetate copolymer/polyamide. If the laminated film is an unstretched or uniaxially stretched film, not only will there be a problem with the mechanical strength of the balloon, but the shape retention ability will also be reduced, and there will also be problems with pitch accuracy during multicolor printing.

In order to produce the biaxially stretched laminated film described above, a coextrusion method is used.

That is, each resin is extruded, laminated in a feed block or T-die, and then rapidly cooled on a roll to form a film to obtain an unstretched sheet, which is then biaxially stretched and heat treated.

The method of biaxial stretching is described in, for example, Japanese Patent Application Laid-Open No. 52-115880.
Either simultaneous biaxial stretching described in JP-A-61-273931 or sequential biaxial stretching described in JP-A-61-273931 may be used. Also,
It may be stretched after film formation using an annular die.

In the case of tenter sequential biaxial stretching, for example, a coextrusion molded sheet is heated to a temperature range of 50°C to 75°C, stretched 2 to 5 times in the machine direction with a roll longitudinal stretching machine, and then stretched by a tenter transverse direction. What is necessary is just to stretch 2 to 5 times in the transverse direction within the range of 60° C. to 95° C. using a stretching machine. Further, in the case of simultaneous biaxial stretching in a tenter or simultaneous biaxial stretching in a tubular film, the film may be stretched 2 to 5 times in each direction simultaneously at 60° C. to 100° C., for example.

In the present invention, the total thickness of the biaxially stretched laminated film is 1
It is 0-30μ, preferably 12-25μ. When the thickness is within this range, it is possible to obtain a balloon that has both excellent shape retention ability and floating retention ability, and has high pinhole resistance.

If it is less than 10μ, gas barrier properties, strength, and shape retention ability are poor. If the field exceeds 30μ, the weight of the balloon becomes large, and as a result, although it has the ability to maintain its shape, it is inferior in its ability to maintain floating.

In the present invention, the thickness of the saponified ethylene vinyl acetate copolymer layer of the biaxially stretched laminated film is 3 to 20 μm, preferably 4 to 15 μm. If it is less than 3μ, the gas barrier properties and shape retention ability will be poor, and if it exceeds 20μ, the pinhole resistance of the biaxially stretched laminated film will be poor. On the other hand, the thickness of the polyamide layer is 3 to 10 microns, preferably 4 to 9 microns. If it is less than 3μ, the pinhole resistance is poor and the
If it exceeds μ, not only will the weight of the balloon increase, but the pinhole resistance improvement effect will be saturated.

Further, in the present invention, in order to further improve the appearance and shape retention ability, metals or ceramics can be vapor-deposited on the biaxially stretched laminated film. The vapor deposition materials include aluminum metal, aluminum oxide,
Examples include silicon oxide and silicon nitride. In addition, films subjected to blank vapor deposition processing (performed under the names of perlite processing, pasta processing, etc.) or stripe vapor deposition can also be used.

Next, the heat sheet resin layer (B) will be explained.

In the present invention, the heat sheet resin is used as high density polyethylene (HDPE), medium density polyethylene (M
DPE), low density polyethylene (LDPE), polypropylene (PP), ethylene-vinyl acetate copolymer (EV
A), ethylene-methacrylate copolymer (EMA)
, ethylene-ethyl acrylate copolymer (EEA)
, ethylene-methacrylate copolymer (EMMA),
Ethylene-ethyl acrylate copolymer (FAA), ethylene-ethyl methacrylate copolymer (EMAA), adhesive polyethylene, ionomer resin, saponified EVA,
Linear low density polyethylene (L-LDPE) or copolymers thereof are used.

The thickness of the heat-sealing layer (the total thickness if it is a multi-layer) is 3 to 30 microns, preferably 10 to 25 microns. When the thickness is within this range, it is possible to obtain a balloon that has both excellent floating retention ability and mechanical strength. If the thickness of the heat sheet layer is less than 3μ, the sealing strength will not be sufficient, and if it exceeds 30μ, the weight of the balloon will be too thick (as a result, it will not float unless the balloon is large). , the thickness of the heat seal layer is
It is preferable to appropriately select from within the above range depending on the size of the balloon, required strength, etc.

Gas barrier resin layer (A) and heat sealing resin layer (
The composite (lamination) in B) may be performed by dry lamination of both layers, or by extrusion lamination or coextrusion in the lamination order of polyamide/saponified ethylene vinyl acetate copolymer/polyamide/heat-sealable resin. Alternatively, a method may be used in which the film is stretched biaxially.

In the present invention, the heat-sealable resin layer (B) does not need to be present on the entire balloon, and may be present only on the sealed portion of the balloon.

However, for boat fishing, extrusion lamination is often adopted due to material costs, processing costs, ease of handling, etc., and a heat-sealable resin layer (B) is often provided over the entire balloon.

The heat seal layer resin (B) does not need to be one layer, and may be provided on both sides of the gas barrier resin layer (A).

If there is only one heat seal layer (B), only a gassho seal can be made, but if two layers are provided as described above, not only a gassho sticker but also an envelope can be pasted, and the finished balloon will have a beautiful appearance. .

In the present invention, a two-wheel stretched PET film or a biaxially stretched nylon film may be laminated as the outermost layer in order to improve heat resistance during heat sealing. In this case, the total thickness is 60
From the viewpoint of buoyancy, it is desirable that the thickness be less than μ, particularly less than 45 μ.

The balloon of the present invention is particularly suitably used for toys and decorations, and the balloon is particularly preferably sized to the extent that it can be filled with a gas such as helium of about 200 d to 60 amps. In the case of a small balloon, it is necessary to make the layer structure as thin as possible, and it is desirable to consider the thickness depending on the size of the balloon.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

The evaluation results of the balloons obtained in the following examples are shown in Table 1.

Example I Preparation of CAE NY6/EVOH/NY6 biaxially stretched laminate film Nylon 6 resin (Tsubamitsudo 1022 manufactured by Mitsubishi Kasei ■)
was extruded from two extruders, and EVOH (ethylene content 32 mo1%, saponification degree 99.6 mo1%, ■
Kuraray's EVAL EP-F 101B) was extruded from another extruder and T was processed in the order of NY6/EVOH/NY6.
- Laminated in a die and then rapidly cooled on a cooling roll at 30° C. to obtain a cast film with a total thickness of 126 μm, each layer having a thickness of 42 μm. After raising the temperature of this film to 50°C, it was stretched 3 times in the machine direction with a roll stretching machine, further stretched 3.5 times in the direction perpendicular to the machine direction with a tenter at 90°C, and then heat treated at 200°C. A biaxially stretched laminated film having a total thickness of 12 μm was obtained. Both sides of this film were subjected to corona treatment to achieve wettability with a wetting reagent of 52 dyn or more.

[B] Printing One side of the above film was printed in six colors.

It printed well without any problems in terms of appearance.

[C,] Preparation of composite film and balloon Isocyanate-based anchor coating agent (Toyo Morton Co., Ltd. AD503/CAT-10) on the above biaxially stretched laminated film layer
After applying 0.2 g/rr1' of solid content and evaporating the solvent, LDPE (Tubatic L-3 manufactured by Mitsubishi Chemical Corporation) was applied.
00) was extruded at a temperature of 320° C. and a film thickness of 15 μm to obtain a composite film.

After aging the above composite film at 40° C. for 2 days, it was heat-sealed at 165° C. to produce a balloon with a diameter of 45 cm as shown in FIG. 1, and helium was injected.

Figure 1 is a longitudinal section of the obtained balloon, and in the figure (
1) is a gas barrier resin layer (NY6/EVOH/NY
6), (2) is a heat-sealable resin layer (LDPE), and (3) is a helium injection port.

Example 2 In Example 1, the obtained composite film was heated at 40°C for 2
After aging for 1 day, gelbolex tester (US military standard MIL-B-131GFED-8TD-10) was used.
1Method Ni12071), 200
A balloon was prepared in the same manner as in Example 1, except that it was used after being bent twice, and helium was injected. However, LDPE
The thickness of the layer was 20μ.

The above bending treatment was performed to evaluate pinhole resistance, and if pinholes occur due to this treatment, the number of days the balloon floats and the number of days it retains its shape will be shortened. Depending on the degree of occurrence, the balloon may not be inflated.

Example 3 An anchor coating agent was applied in the same manner as in Example 1, except that aluminum metal was vacuum-deposited on the biaxially stretched laminated film, and a composite film was obtained.

Next, the composite film was aged at 40° C. for 2 days, and then a balloon was prepared in the same manner as in Example 1, and helium was injected.

Comparative Example 1 A balloon was produced in the same manner as in Example 1, except that the thickness of the LDPE was changed to 50 μm, and helium was injected.

Comparative Example 2 Aluminum metal was vacuum-deposited on a nylon film with a thickness of 12μ obtained by biaxial stretching 3×3 times, and an anchor coating agent was applied under the same conditions as in Example 1, and the solvent was evaporated. PP (F-8090 manufactured by Chisso ■) was extruded at a temperature of 300° C. and a film thickness of 15 μm to obtain a composite film.

After aging the above composite film at 40°C for 2 days, it was subjected to a bending treatment in the same manner as in Example 2, and then a balloon was prepared in the same manner as in Example 1, and helium was injected.

Comparative Example 3 Saponified ethylene-vinyl acetate copolymer (ethylene content 32 mol%) with a film thickness of 15 μ obtained by biaxial stretching 3×3 times
) One side of the film was corona-treated to achieve a wettability of 52 dyn or more with a wetting reagent.

When one side of the above film was printed in six colors to evaluate the printability, some printing defects were observed.

Using the above film, a composite film was obtained in the same manner as in Example 1, and a bending treatment was performed in the same manner as in Example 2. Then, a balloon was prepared in the same manner as in Example 1, and helium was injected.

However, the balloon did not inflate due to pinholes caused by the bending process.

(Hereinafter, blank space) [Effects of the invention] According to the present invention, it has excellent floating retention ability and shape retention ability,
A balloon with improved pinhole resistance and printability is provided. The balloon of the present invention can be formed into a spheroid, a sphere, a cylinder, a cone, a tetrahedron, a cube, an airplane, etc., and can be used as a toy, promotional item, decoration in a shop window, or outdoors. It can be suitably used for decoration of signboards, etc.

[Brief explanation of the drawing]

FIG. 1 is a cross-sectional view of an example of the balloon of the present invention. In the figure, (1) shows a gas barrier resin layer, (2) a human sealing resin layer, and (3) a helium injection port. Applicant Mitsubishi Monsanto Chemicals Co., Ltd. Agent Patent Attorney Oka 1) Kazuhiko

Claims (1)

[Claims] (1) Gas barrier resin layer (A
) and a heat-sealable resin layer (B) with a thickness of 3 to 30μ, and a gas barrier resin layer (A).
However, a polyamide layer with a thickness of 3 to 10μ, a saponified ethylene-vinyl acetate copolymer layer with a thickness of 3 to 20μ, and a layer of saponified ethylene-vinyl acetate copolymer with a thickness of 3
A balloon characterized in that it is a biaxially stretched laminated film in which polyamide layers of ~10 μm are laminated in the listed order.