JP3972159B2 - Film for vapor deposition balloon - Google Patents

Description

実施例１で得られたフィルムの物性値を以下に列挙する。
【００３０】
・平均厚み：２０．７μｍ
・ヘイズ：２．５％（ASTM D-1003に従い測定）
・引張強度：ＭＤ（960 kg/cm²）、ＴＤ（1397 kg/cm²）
・引張伸度：ＭＤ（160 ％）、ＴＤ（85 ％）
（引張強度、引張伸度はいずれもJIS K-6732に従い測定）
・滑性（静摩擦／動摩擦）：NY-NY（0.58/0.51）、LL-LL（0.62/0.51）
（ASTM D-1894に従い測定）
・熱収縮率（１００℃、温水×３０Ｓで測定）：ＭＤ(2.3%)、ＴＤ(1.3%)
・貫孔強度：ＮＹ面（0.67kg)、ＬＬ面（0.60kg)（JIS P-8116に従い測定)
・衝撃強度：ＮＹ面（8.3kg・cm)、ＬＬ面（9.0kg・cm)（打ち抜き式インパクトテスター；小球にて測定)
・シール強度（圧力=2kg/cm²；時間＝１秒）：
120℃(1.2kg/cm)、130℃(2.1kg/cm)、140℃(2.2kg/cm)、150℃(2.3kg/cm)、160℃(2.3kg/cm)、170℃（2.3kg/cm)
・酸素透過率：４３cc/m²・24h・20℃×65%RH（ASTM D-3985に従い測定）
・ぬれ指数：ＬＬ面（36dyn/cm）、ＮＹ面（50dyn/cm）（JIS K-6768に従い測定)
実施例４
実施例１で得たフィルムを巾１００ｃｍに長尺帯状にカットし、その幅方向の中心から一方に巾５０ｃｍ、厚さ４００Åのアルミニウムによる金属蒸着層を（Ａ）層の表面に形成した。こうして得たバルーンフィルムのヒートシール層同志をヒートシールして球状に形成し、１．２気圧のヘリウムガスを充填して不透明状の金属蒸着層を有するバルーンを得た。こうして得たバルーンは意匠効果も良好である上に、７日間空中に浮遊していた。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a film for vapor deposition balloon.
[0002]
[Prior art and problems]
As the vapor deposition balloon film, a laminated film having a three-layer structure of 6-nylon layer / adhesive resin layer / LLDPE layer has been used as the vapor deposition balloon film.
[0003]
A film having a five-layer structure comprising a polyamide resin layer, an ethylene-vinyl acetate copolymer saponified material layer, a polyamide resin layer, an adhesive resin layer and a polyolefin resin layer has also been proposed (Japanese Patent Laid-Open No. 7-290650). Issue gazette).
[0004]
However, these films have a problem that the film curls.
[0005]
An object of this invention is to provide the film for vapor deposition balloons which a film does not curl.
[0006]
[Means for Solving the Problems]
The present invention relates to a film for vapor deposition balloon formed by laminating five layers of polyamide resin layer / polyolefin layer / polyamide resin layer / adhesive resin layer / LLDPE layer.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
In the vapor deposition balloon film of the present invention, the polyamide resin layer is composed of 6-nylon (poly-ε-caprolactam), 66-nylon (polyhexamethylene adipamide), 12-nylon (12-aminododecanoic acid lactam). Polymer), crystalline nylon such as 6-66 copoly nylon, 6-12 copoly nylon or amorphous nylon, preferably about 70 to 95% by weight of crystalline nylon and about 30 to 5% by weight of amorphous nylon, More preferably, it contains about 80 to 90% by weight of crystalline nylon and about 20 to 10% by weight of amorphous nylon. 6-66 copolynylon is a copolymer of 6-nylon (poly-ε-caprolactam) and 66 nylon (polyhexamethylene adipamide), and the proportion of 6-nylon is about 30 mol% or more, preferably 50 % Or more, more preferably about 70 mol% or more. The molecular weight of nylon is about 13,000 to 33000. The two polyamide-based resin layers may be the same or different as long as they contain the above components. The thickness of the polyamide resin layer is about 1 to 15 μm, preferably about 3 to 10 μm. Examples of the amorphous nylon include copolymers or terpolymers of dicarboxylic acids such as terephthalic acid and isophthalic acid and diamines such as hexamethylenediamine.
[0008]
The polyolefin layer is not particularly limited as long as the two polyamide-based resin layers can be bonded to each other, but is preferably a polyolefin such as polyethylene or polypropylene, more preferably linear low density polyethylene (LLDPE) and / or low density polyethylene (LDPE). ), Especially LLDPE. The thickness of the polyolefin layer is about 1 to 6 μm, preferably about 1.5 to 4 μm. In addition to polyolefin such as LLDPE, a polyolefin-based adhesive resin such as LLDPE treated by graft reaction may be used in the polyolefin layer instead of polyolefin or together with polyolefin. The polyolefin layer preferably comprises a polyolefin-based adhesive resin.
[0009]
The adhesive resin layer is not particularly limited as long as the polyamide resin layer and the seal layer can be bonded, but is preferably LLDPE treated by a graft reaction. The thickness of the adhesive resin layer is about 1 to 6 μm, preferably about 1.5 to 3 μm.
[0010]
The sealing layer comprises LLDPE or LDPE, in particular LLDPE. The thickness of the sealing layer is about 2 to 20 μm, preferably about 5 to 10 μm.
[0011]
The overall thickness of the balloon film of the present invention is about 10 to 70 μm, preferably about 15 to 35 μm.
[0012]
The polyamide-based multilayer shrink film of the present invention is preferably a flat film. This film may be coextruded in a flat shape from a T die and sequentially biaxially stretched. Although there is no restriction | limiting in particular about film forming, Generally, it can carry out by extrusion casting on the cooled chill roll. The film of the present invention is obtained by sequentially biaxially stretching the film thus formed. For stretching, for example, longitudinal stretching by a roll stretching machine and transverse stretching by a tenter stretching machine are performed.
[0013]
The draw ratio is preferably about 1.2 to 5 times in the longitudinal direction and about 2.5 to 5 times in the transverse direction. The stretching temperature is about 60 to 120 ° C in the longitudinal direction, preferably about 70 to 100 ° C, and about 70 to 180 ° C, preferably about 100 to 160 ° C in the lateral direction.
[0014]
After stretching, heat treatment is performed as necessary. The heat treatment method is not particularly limited, but is generally performed in a continuous process following the transverse stretching by a tenter stretching machine. When the heat treatment is performed, it can be performed in a state of being reduced (relaxed) within 20% in the width direction, preferably 3 to 10%. You may set the width more than time. The heat treatment conditions are, for example, less than 150 ° C., preferably in the range of about 80 to 130 ° C. with a tenter stretching machine, and if necessary, in a state reduced to about 20% in the width direction, preferably about 3 to 10%. be able to. The heat shrinkage is performed for the purpose of preventing spontaneous shrinkage.
[0015]
The multilayer film which concerns on this invention is used suitably as a film for vapor deposition balloons. Specifically, a vapor deposition layer of aluminum oxide, silicon dioxide, and other various metals (aluminum foil) can be provided on the entire surface or part of the polyamide resin layer of the film of the present invention. When such a metal vapor deposition layer is partially formed, it can be formed anywhere, but preferably the obtained film is cut into a long band shape and from the center in the width direction to one side. It is desirable to form a metal vapor deposition layer while the other remains a transparent film. This is convenient because it is very easy to form a balloon having a metal vapor deposition layer in which the half surface remains transparent and the other half surface is opaque. Moreover, according to such a film, it is possible to easily form a spherical balloon having a metal vapor deposition layer in which the hemispherical surface remains transparent and the other hemispherical surface is opaque.
[0016]
The balloon film of the present invention preferably has the following physical properties:
The heat seal strength is 1.0 kg / cm or more, preferably 1.5 kg / cm or more;
Haze (measured according to ASTM D-1003) is 1.0 to 7.0%, preferably 2.0 to 5.0%;
-Tensile strength: MD (800-1500 kg / cm < ² >), TD (800-1500 kg / cm < ² >);
-Tensile elongation: MD (80-180%), TD (80-180%);
(Tensile strength and tensile elongation are both measured according to JIS K-6732)
Heat shrinkage (measured at 100 ° C., warm water × 30S): MD (0 to 5.0%), TD (0 to 5.0%);
-Through hole strength: NY surface (0.5 kg or more), LL surface (0.5 kg) (measured according to JIS P-8116);
Impact strength: NY surface (5.0 kg · cm or more), LL surface (5.0 kg · cm or more) (punch-type impact tester; measured with a small ball);
・ Seal strength (pressure = 2kg / cm ² ; time = 1 second):
120 ° C (1.0 kg / cm or more), 130 ° C (1.0 kg / cm or more), 140 ° C (1.5 kg / cm or more),
150 ° C. (1.5 kg / cm or more), 160 ° C. (1.5 kg / cm or more), 170 ° C. (1.5 kg / cm or more);
・ Oxygen permeability: 100cc / m ²・ 24h ・ 20 ℃ × 65% RH or less (measured according to ASTM D-3985);
-Wetting index: NY surface (45 dyn / cm or more) (measured according to JIS K-6768);
-Vapor deposition strength (peeling strength between NY surface and vapor deposition portion) is 20 g / 15 mm or more, preferably 50 g / 15 mm or more.
[0017]
The balloon of the present invention can be produced by heat-sealing the heat-seal layers of the balloon film so as to be formed into an arbitrary shape and size such as a spherical shape and an ellipsoid shape.
[0018]
【Example】
Hereinafter, the present invention will be described in more detail based on examples and comparative examples.
[0019]
[Curling evaluation method]
Measurement temperature and humidity: 20 ° C x 50% RH
(1) Make a cut in the diagonal line of 100mm x 100mm film.
[0020]
(2) Measure the width and height of the film when rounded in the MD and TD directions.
[0021]
The larger the standard and width, the lower the curling property (the better the quality)
・ The higher the height, the lower the curling property (the better the quality)
This is because when the curl property is strong, the curl is rounded down and the width and height are reduced.
[0022]
Example 1
A five-layer laminated film was manufactured using the following raw materials.
[0023]
(1) Raw material:
Polyamide resin layer (hereinafter referred to as “A” layer) = 6-nylon (80% by weight) and amorphous nylon (20% by weight)
-Polyolefin layer (hereinafter referred to as "B" layer) = LLDPE-based adhesive resin-Adhesive resin layer (hereinafter referred to as "C" layer) = LLDPE-based adhesive resin-Seal layer (hereinafter referred to as "D" layer) = LLDPE
(2) Manufacturing method The components (A / B / A / C / D) of each of the above layers were coextruded from a T-die to a chill roll in which cooling water circulates to obtain a flat five-layer film. Thereafter, the film is stretched three times longitudinally by a roll stretching machine at 80 ° C., further stretched 3.8 times by a tenter stretching machine in an atmosphere at 120 ° C., and then the width is reduced by about 4% by the tenter stretching machine. Then, it was heat-set in an atmosphere at 200 ° C. The thickness of the obtained film was A / B / A / C / D = 4/2/4/2/8 (μm).
[0024]
The physical properties of the obtained film are shown in Table 1.
[0025]
Example 2
A laminated film having a five-layer structure having a thickness of A / B / A / C / D = 4/2/4/2/8 (μm) is obtained in the same manner as in Example 1 except that the following raw materials are used. Manufactured. The physical properties of the obtained film are shown in Table 1.
[0026]
A layer = 6-nylon (80 wt%) and amorphous nylon (20 wt%)
B layer = LLDPE-based adhesive resin (50 wt%) + LLDPE (50 wt%)
C layer = LLDPE-based adhesive resin D layer = LLDPE
Example 3
A laminated film having a five-layer structure having a thickness of A / B / A / C / D = 6/3/6/2/18 (μm) is obtained in the same manner as in Example 1 except that the following raw materials are used. Manufactured. The physical properties of the obtained film are shown in Table 1.
[0027]
A layer = 6-nylon (80 wt%) and amorphous nylon (20 wt%)
B layer = LLDPE-based adhesive resin C layer = LLDPE-based adhesive resin D layer = LLDPE
Comparative Example 1
A laminated film having a three-layer structure having a thickness of A / C / D = 10/2/10 (μm) was produced in the same manner as in Example 1 except that the following raw materials were used. The curl measurement results of the obtained film are shown in Table 2.
[0028]
A layer = 6-nylon (80 wt%) and amorphous nylon (20 wt%)
C layer = LLDPE-based adhesive resin D layer = LLDPE
Test example 1
Table 2 shows the curl measurement results of the films obtained in Example 1 and Comparative Example 1.
[0029]
[Table 2]

The physical property values of the film obtained in Example 1 are listed below.
[0030]
・ Average thickness: 20.7μm
・ Haze: 2.5% (measured according to ASTM D-1003)
・ Tensile strength: MD (960 kg / cm ² ), TD (1397 kg / cm ² )
・ Tensile elongation: MD (160%), TD (85%)
(Tensile strength and tensile elongation are both measured according to JIS K-6732)
・ Lubricity (static friction / dynamic friction): NY-NY (0.58 / 0.51), LL-LL (0.62 / 0.51)
(Measured according to ASTM D-1894)
-Heat shrinkage (measured at 100 ° C, warm water x 30S): MD (2.3%), TD (1.3%)
・ Through hole strength: NY surface (0.67kg), LL surface (0.60kg) (measured according to JIS P-8116)
・ Impact strength: NY surface (8.3kg ・ cm), LL surface (9.0kg ・ cm) (Punched impact tester; measured with a small ball)
・ Seal strength (pressure = 2kg / cm ² ; time = 1 second):
120 ℃ (1.2kg / cm), 130 ℃ (2.1kg / cm), 140 ℃ (2.2kg / cm), 150 ℃ (2.3kg / cm), 160 ℃ (2.3kg / cm), 170 ℃ (2.3kg) /cm)
・ Oxygen permeability: 43cc / m ²・ 24h ・ 20 ℃ × 65% RH (measured according to ASTM D-3985)
-Wetting index: LL surface (36 dyn / cm), NY surface (50 dyn / cm) (measured according to JIS K-6768)
Example 4
The film obtained in Example 1 was cut into a long strip having a width of 100 cm, and a metal vapor deposition layer of aluminum having a width of 50 cm and a thickness of 400 mm was formed on the surface of the layer (A). The heat seal layers of the balloon film thus obtained were heat-sealed to form a spherical shape, and filled with 1.2 atm of helium gas to obtain a balloon having an opaque metal deposition layer. The balloon thus obtained had a good design effect and was floating in the air for 7 days.

Claims (6)

Vapor deposition balloon in which a metal vapor deposition layer is provided entirely or partially on a polyamide resin layer on the surface of a film formed by laminating five layers of polyamide resin layer / polyolefin layer / polyamide resin layer / adhesive resin layer / sealing layer. The thickness of each layer of polyamide resin layer / polyolefin layer / polyamide resin layer / adhesive resin layer / sealing layer is 1-15 μm / 1-6 μm / 1-15 μm / 1-6 μm / 2-20 μm. The film for vapor deposition balloons whose whole thickness of a 5 layer lamination film is 15-35 micrometers . The film for vapor deposition balloon according to claim 1, wherein the polyamide resin layer is a mixed resin layer containing 70 to 95% by weight of crystalline nylon and 30 to 5% by weight of amorphous nylon . The film for vapor deposition balloons of Claim 1 or 2 in which a metal vapor deposition layer is formed, and a half surface is transparent, and the other half surface has a metal vapor deposition layer. The balloon which has a film for vapor deposition balloons in any one of Claims 1-3 . Heat-seal layers of the film for vapor deposition balloon according to any one of claims 1 to 3 are heat-sealed and formed into an arbitrary shape or size such as a spherical shape or an ellipsoidal shape, and a vapor deposition balloon is produced. Method. Vapor deposition balloon in which a metal vapor deposition layer is provided entirely or partially on a polyamide resin layer on the surface of a film formed by laminating five layers of polyamide resin layer / polyolefin layer / polyamide resin layer / adhesive resin layer / sealing layer. (1) Polyamide resin / polyolefin / polyamide resin / adhesive resin / sealing layer resin is co-extruded in a flat shape from a T-die, and the thickness of each layer is 1 to 15 μm / 1 to 6 μm, respectively. / 1 to 15 μm / 1 to 6 μm / 2 to 20 μm, and the bilayered film is sequentially biaxially stretched so that the total thickness of the five-layer laminated film is 15 to 35 μm. (2) A metal vapor deposition layer is formed in the whole surface or a part of surface polyamide system resin layer, The manufacturing method characterized by the above-mentioned.