JPH0741571A - Metallizing polyethylene film - Google Patents

Abstract

PURPOSE:To obtain a metallizing polyethylene film excellent in low-temperature heat sealability, adhesiveness of metallized layer and printability and suitability for lamination on metallized layer, being free from poor roll form such as wrinkling and bump formation during winding in the fabrication and metallizing of film. CONSTITUTION:The film is made from a mixture of 100 pts.wt. composition comprising 60-95wt.% ethylene/alpha-olefin copolymer of a density of 0.910-0.935g/cm<3> and 5-40wt.% low-density polyethylene of a density of 0.910-0.940g/cm<3> with 0.01-0.2 pt.wt. phenolic antioxidant of a molecular weight of 500 or above, such as tris(2,4-di-t-butylphenyl)phosphite, 0.01-0.1 pt.wt. phosphorous antioxidant of a molecular weight of 500 or above, 0.01-0.1 pt.wt. hydrotalcite, and 0.05-0.5 pt.wt. antiblocking agent. It has a load of 400gf/cm or above at an elongation of 5% in the machine direction.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention is excellent in low-temperature heat-sealing property, adhesive strength of vapor-deposited film, printability on a vapor-deposited surface and suitability for lamination, and has a "wrinkle" during film winding during film forming or vapor deposition processing. The present invention relates to a polyethylene-based film for metal vapor deposition, which does not have a winding defect such as "rolled gall" and has a good vapor deposition appearance.

[0002]

2. Description of the Related Art Plastic films with metal vapor deposition are used as packaging materials for food packaging, clothing packaging, gold and silver threads, labels,
Widely used in electrical materials such as stickers and capacitors. In particular, aluminum vapor-deposited films are used in large quantities as packaging materials. The reason is that the contents can be protected by blocking light and oxygen, a beautiful metallic luster can be easily obtained, and the cost and weight are lower than those of metal foil. In such a metal vapor deposition film, good adhesive strength between the film and the vapor deposition layer is required, and the metal vapor deposition surface can be printed,
It is widely practiced to apply a top coat to the vapor-deposited surface to protect the vapor-deposited surface, or to apply an anchor coating agent and then extrude or dry-laminate a resin such as polyolefin, nylon, polyester, EVAL, etc. It must have printability and laminating suitability. Further, the vapor-deposited substrate is usually used as the innermost layer of the packaging material, and it is necessary to have good low-temperature heat sealability from the viewpoint of high-speed productivity of the packaging material. Needless to say, the vapor deposition must have an excellent appearance such as a uniform vapor deposition and a beautiful gloss.

However, the polyolefin film is inferior in the adhesive strength between the film and the vapor deposition layer (hereinafter sometimes referred to as "vapor deposition strength"), and various proposals have been made to improve the adhesiveness. For example, in JP-A-56-167732, a total amount of an antioxidant, a lubricant, a hydrochloric acid scavenger and an antistatic agent is 0.2 per 100 parts by weight of a polyolefin resin.
A resin composition added by parts by weight or less has been proposed. As examples, various antioxidants were added to high density polyethylene, erucic acid amide as a lubricant, calcium stearate as a hydrochloric acid scavenger, and alkylamine as an antistatic agent. The composition is described. Further, in the above publication,
The poor metal vapor deposition strength of the polyolefin film is due to the surface migration (bleed-out) of the additive for polyolefin, and the deterioration of the printability and laminating suitability of the metal vapor deposition surface is due to the polyolefin being stored in the wound state of the film after vapor deposition. It is described as being caused by the transfer of the additive in the film to the metal vapor deposition surface. However, it is difficult to prevent the deterioration of the vapor deposition strength and the printability of the vapor deposition surface by the limitation of the above additives, and since the high-density polyethylene is slightly lacking in the film processability, it is inferior in the fine smoothness of the film surface. It lacks gloss on the vapor deposition surface and is not necessarily suitable as a vapor deposition substrate. Further, in JP-A-59-11249, 0.01 to 0.2 parts by weight of an antioxidant having a melting point of 80 ° C. or more and 0.01 to 0.5 parts of an anti-blocking agent are used with respect to 100 parts by weight of a polypropylene resin. A resin composition added by weight has been proposed. Further, Japanese Patent Laid-Open No. 59-25829 discloses that
Propylene / α-with specific melt flow rate ratio
A composition of 80 to 96% by weight of an olefin copolymer and 4 to 20% by weight of high density polyethylene, and 0.01 to 0.3% by weight of a phenol or phosphorus antioxidant having a molecular weight of 500 or more as an additive. , A metal-substituted zeolite of 0.
A composition containing 0.1 to 0.4% by weight has been proposed,
It is described that fatty acid derivatives such as higher fatty acid salts, fatty acid amides, fatty acid esters, and fatty acid amine derivatives most adversely affect the adhesiveness of the vapor deposition layer and the printability of the vapor deposition surface.

However, the above publications relate to a polyolefin film for metal vapor deposition containing high density polyethylene or polypropylene as a main component, and among the polyolefin films, mechanical strength such as tear strength, tensile strength, elongation, impact resistance, heat resistance, heat resistance, etc. Until now, no metal vapor deposition film based on a crystalline ethylene / α-olefin copolymer (linear low density polyethylene) having excellent seal strength and hot tack property has been proposed.

[0005]

The present invention is excellent in low-temperature heat-sealing property, vapor deposition strength, printability on a vapor deposition surface and suitability for lamination, and has no wrinkles or winding when film is wound during film forming or vapor deposition processing. There are no winding defects such as humps,
And ethylene / α for metal deposition with excellent vapor deposition appearance such as gloss
-Olefin copolymer films.

[0006]

[Means for Solving the Problems] The inventors of the present invention have diligently studied a metal vapor-deposited film based on an ethylene / α-olefin copolymer, which is excellent in mechanical strength, heat seal strength and hot tack property among polyolefin films. As a result, all of the above problems are solved by using a film made of a composition of an ethylene / α-olefin copolymer having a specific density in which the kind and amount of additives are limited and low density polyethylene as a vapor deposition substrate. The inventors have found what can be done and have completed the present invention.

That is, the present invention has a density of 0.910 to 0.93.
Copolymer of 5 g / cm ³ of ethylene and α-olefin 60 to 95% by weight and density of 0.910 to 0.940 g / c
0.01 to 0.2 parts by weight of a phenolic antioxidant having a molecular weight of 500 or more and a molecular weight of 500 or more with respect to 100 parts by weight of a composition (1) composed of 5 to 40% by weight of m ³ of low-density polyethylene. 0.01 to 0.1 of the phosphorus-based antioxidant
Parts by weight, 0.01 to 0.1 parts by weight of hydrotalcite and 0.05 to 0.5 parts by weight of an anti-blocking agent are added, and the load at 5% elongation in the machine direction is 400 gf.
It is a polyethylene-based film for metal vapor deposition of not less than / cm.

The present invention will be described in detail below.

The low density polyethylene used as a component of the composition (1) in the film for vapor deposition of the present invention is blended for the purpose of improving the processability of the ethylene / α-olefin copolymer, and its density is 0.910-0.
940 g / cm ³ , preferably 0.915 to 0.930
It is a homopolymer of ethylene produced by a high pressure method of g / cm ³ . It is difficult to industrially produce a product having a density outside this range by the high pressure method. If high-density polyethylene with a density of more than 0.940 g / cm ³ is used instead of low-density polyethylene, the film processability deteriorates and the unevenness of the film surface becomes severe. Is not preferable and the high speed productivity of the packaging material is lacking, which is not preferable.

The α-olefin which is a comonomer of the ethylene / α-olefin copolymer used as a component of the composition (1) in the film for vapor deposition of the present invention has the general formula R-CH = CH ₂ (wherein R is Represents an alkyl group having 3 to 16 carbon atoms, and specific examples thereof include propylene, 1-butene, 1-hexene, 1-decene, 1-octene and 4-methyl-1-. Pentene, 1-nonene, 4-methyl-1-hexene and the like can be mentioned. The comonomer content is not particularly limited, but is 0.1
-10 mol% is preferable.

The ethylene / α-olefin copolymer used as the component of the composition (1) in the film for vapor deposition of the present invention has a density (JIS K6760) of 0.
910 to 0.935 g / cm ³ , preferably 0.920
Is about 0.930 g / cm ³ . When the density of the copolymer is less than 0.910 g / cm ³ , blocking tends to occur as a result of an increase in low molecular weight components in the copolymer, the vapor deposition strength is lowered, and the low molecular weight in the wound state of the vapor deposition film is low. Transferring the components to the vapor deposition surface results in poor printability and laminating suitability on the vapor deposition surface. Further, as a result of lowering the rigidity and heat resistance of the film, the film tends to stretch due to the winding tension during film processing or vapor deposition processing, and wrinkles or lumps easily occur. Particularly, in the continuous vacuum vapor deposition method widely adopted as the vapor deposition method, the vapor deposition cooling roll 2 shown in FIG. 1 is used.
If the film substrate is not closely aligned with the film, un-deposited lines (rails) will be generated in the transverse direction of the film, so it is necessary to apply a higher tension than when processing the film. Therefore, if the film rigidity decreases, the tension will be maintained. As a result, undeposited lines are likely to occur, and at the same time wrinkles and lumps are likely to occur on the film due to deformation of the film due to tension. Further, since the cooling roll has a relatively high temperature due to the radiant heat of the molten metal, if the heat resistance of the film is inferior, the unevenness of vapor deposition during the vapor deposition process becomes more severe. In order to prevent wrinkles during winding, uneven lumps and unevenness of vapor deposition during vapor deposition due to a decrease in film rigidity such as this, fatty acid amide, which is most effective as a lubricant to add slipperiness to the film, is added and rolled with low tension. When taken, the winding shape is improved, but the addition of fatty acid amide deteriorates the vapor deposition strength, the printability of the vapor deposition surface and the suitability for lamination, and the vapor deposition unevenness is not improved. If the density of the copolymer exceeds 0.935 g / cm ³ , the low-temperature heat-sealing property is deteriorated and the high-speed productivity of the packaging material is lacking, which is not preferable.

The mixing ratio of the ethylene / α-olefin copolymer in the composition (1) is 60 to 95% by weight, preferably 70 to 90% by weight. If it is less than this range, the mechanical strength such as tear strength, tensile strength, elongation, impact resistance and the like, which are the characteristics of the ethylene / α-olefin copolymer film, and heat seal strength are lowered, and if it exceeds this range, it is processed. The sex becomes worse.

In the vapor-deposited film of the present invention, the type of the additive added to the composition (1) is not limited, or even if the type is limited, if the addition amount is too large, the vapor deposition strength decreases and printing on the vapor-deposited surface occurs. And the suitability for lamination are impaired. However, if the type and amount of additives are too limited, gel will be generated during film formation, blocking will occur in the film, and the extruder and die will be corroded, and the vapor deposition layer will be corroded by acid, resulting in impaired beauty. Or For this reason, it is important to select the type and amount of additive. Examples of the phenol-based antioxidant having a molecular weight of 500 or more added to the composition (1) in the vapor-deposited film of the present invention include monophenol-based, bisphenol-based, thiobisphenol-based, and trisphenol-based antioxidants, More specifically, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-
Butylanilino) -1,3,5-triazine (for example, trade name Irganox 565 from Nippon Ciba Geigy)
Is marketed as. ), 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (commercially available from Nippon Ciba Geigy Co., Ltd. under the trade name Irganox 1035). ), Octadecyl-3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate (commercially available from Nippon Ciba Geigy Co., Ltd. under the trade name Irganox 1076), 1,3,5-trimethyl-2,4,6-tris (3,5-di). -T-butyl-4-hydroxybenzyl) benzene (commercially available from Nippon Ciba Geigy Co., Ltd. under the trade name Irganox 1330), tris- (3,5-di-t-butyl-4-hydroxybenzyl). -Isocyanurate (commercially available from Nippon Ciba Geigy Co., Ltd. under the trade name Irganox 3114), 1,1,3-
Tris- (2-methyl-4-hydroxy-5-t-butylphenyl) butane (for example, Adeka Argus Chemical Co., Ltd.)
Marketed under the trade name MARK AO-30. ), Tris- (4-t-butyl-2,6-di-methyl-3-hydroxybenzyl) isocyanurate (for example, trade name Cyan from Am. Cyanamid Co., Ltd.).
It is commercially available as ox1790. ), 1,3,5-
Trimethyl-2,4,6-tris- (3,5-di-t-
Butyl-4-hydroxybenzyl) benzene (for example, trade name SEENOX 326M from Shiraishi Calcium Co., Ltd.)
Is marketed as. ), 2-t-butyl-6-
(3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate (commercially available from Sumitomo Chemical Co., Ltd. under the trade name of Sumilizer GM), 3, 9-bis [2- [3-
(3-t-butyl-4-hydroxy-5-me
thyl phenyl) propionyloxy]
-1,1-dimethyl ethyl] -2,4
8,10-tetraoxaspiro [5,5] un
decane (eg Sumitomo Chemical Co., Ltd. under the trade name Sum
It is commercially available as ilizer GA-80. ) And the like, and these are used alone or as a mixture of two or more kinds. Among the above phenolic antioxidants, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (commercially available from Nippon Ciba Geigy Co., Ltd. under the trade name Irganox 1076). Is most preferred.

A specific example of the phosphorus-based antioxidant having a molecular weight of 500 or more added to the composition (1) in the vapor-deposited film of the present invention is tris (2,4-di-t-butylphenyl) phosphite ( For example, it is marketed by Nippon Ciba Geigy Co., Ltd. under the trade name IRGAFOS168.), Tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene phosphonite (for example, a product from Nippon Ciba Geigy Co., Ltd.). Name IRGAFOS
It is commercially available as P-EPQ FF. ), Tris (nonylphenyl) phosphite (commercially available from ADEKA ARGUS CHEMICALS CO., LTD. Under the trade name MARK 1178), distearyl pentaerythritol-di-phosphite (e.g. from ADEKA ARGUS CHEMICAL CO., LTD. It is commercially available as MARK PEP-8), di (2,4-di-t-butylphenyl)-
Pentaerythritol-di-phosphite (for example, trade name MARK PEP- from Adeka Argus Chemical Co., Ltd.)
24 is commercially available. ), Di (nonylphenyl)
Pentaerythritol-di-phosphite (for example, trade name MARK PEP- from Adeka Argus Chemical Co., Ltd.)
It is commercially available as 4C. ), Phenyl-bisphenol A pentaerythritol-di-phosphite (trade name MARK P from Adeka Argus Chemical Co., Ltd.)
It is commercially available as EP-2. ), Sodium bis (4-t-butylphenyl) phosphate (for example, trade name MARK NA-1 from Adeka Argus Chemical Co., Ltd.)
It is marketed as 0. ), Bis (2,6-di-t-
Butyl-4-methylphenyl) pentaerythritol-
Di-Phosphite (eg ADEKA ARGUS CHEMICAL CO., LTD.
Marketed under the trade name ADEKA STAB PEP-36. ) And the like, which are used alone or as a mixture of two or more kinds. In the above phosphorus-based antioxidant,
Tris (2,4-di-t-butylphenyl) phosphite (trade name IRG from Nippon Ciba Geigy Co., Ltd.)
It is commercially available as AFOS168. ), And tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene phosphonite (commercially available from Nippon Ciba Geigy Co., Ltd. under the trade name IRGAFOS P-EPQFF). preferable.

The above-mentioned antioxidant is added in the composition (1) 1
0.01 to 0.01 parts by weight of phenolic antioxidant
0.2 parts by weight, preferably 0.05 to 0.1 parts by weight, 0.01 to 0.1, preferably 0.05
.About.0.09 parts by weight. If the amount added is less than the range, the antioxidative ability is insufficient and gel is frequently generated during film forming, resulting in poor molding stability. If the amount exceeds the range, vapor deposition strength and printability on the vapor deposition surface / laminating suitability deteriorate. Further, an antioxidant having a molecular weight of less than 500 is liable to be volatilized by heat during film forming and vapor deposition, and is inferior in expression of antioxidant ability,
In addition, the bleed-out deteriorates the appearance of the vapor deposition, and the vapor deposition strength and the printability and laminating suitability of the vapor deposition surface deteriorate.
The above-mentioned antioxidant is required to be used in combination with a phenol type and an adjacent type. By using the combined type, the antioxidant ability is improved, and the total addition amount of the antioxidant is suppressed to reduce vapor deposition strength and printability of the vapor deposition surface. It is possible to prevent a decrease in the suitability for lamination. As a phosphorus-based antioxidant, tris (2,4-di-t)
When -butylphenyl) phosphite is used, its addition amount is particularly limited and is preferably 0.01 to 0.05 parts by weight. If the amount added exceeds 0.05 part by weight, bleed-out may be severely caused, and vapor deposition unevenness may occur, and vapor deposition strength may be reduced depending on film processing conditions and the like.

The hydrotalcite added to the composition in the film for vapor deposition of the present invention has the general formula M _1-x L
_x (OH) ₂ A _{x / n} · mH ₂ O (where M is Mg ²⁺ , Mn
²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Zn ^{2+ and} other divalent metals, L is Al ³⁺ , Fe ³⁺ , Cr ³⁺ , Co ³⁺ , In ^{3 +}
Trivalent metals such as A, OH ⁻ , F ⁻ , Cl ⁻ , Br ⁻ , N
O ₃ ⁻ , CO ₃ ²⁻ , SO ₄ ²⁻ , Fe (CN) ₆ ³⁻ , CH ₃ CO
An n-valent anion such as O ⁻ , oxalate ion, and salitate ion, and x represents a number in the range of 0 <x ≦ 0.33. )
And is used as a neutralizing agent for the acidic substance of the catalyst residue in the ethylene / α-olefin copolymer in the composition (1). Specifically, it is Mg ₆ Al ₂ (O
H) Mg, a natural mineral having a composition of ₁₆ CO ₃ .4H ₂ O
Examples thereof include synthetic hydrotalcite having a composition of _4.5 Al ₂ (OH) ₁₃ CO ₃ .3.5H ₂ O (commercially available under the trade name DHT-4A from Kyowa Chemical Industry Co., Ltd.) and the like. .

The amount of hydrotalcite added is 0.01 to 0.1 part by weight, preferably 0.02 to 0.06 part by weight, based on 100 parts by weight of the composition. If the amount added is less than the range, the neutralizing ability will be insufficient, and as a result, acidic substances in the catalyst residue may corrode the extruder or die, and the vapor deposition layer may be corroded by acid, impairing the beautiful appearance. Even if the amount added exceeds this range, there is no effect of increasing the amount added, leading to cost increase, and if a large amount is added, the gloss of the vapor-deposited layer decreases due to the rough surface of the film.

Specific examples of the anti-blocking agent added to the composition (1) in the vapor deposition film of the present invention include kaolinite, decalite, nacrite, halloysite, hydrohalloysite, kaolin such as allophane, aluminosilicate and the like. Examples thereof include natural and synthetic zeolites and their derivatives, silicon oxide, aluminum oxide, calcium carbonate, barium sulfate and the like.

The amount of the antiblocking agent added is 0.05 to 0.5 part by weight, preferably 0.1 to 0.4 part by weight, relative to 100 parts by weight of the composition (1). If the addition amount is less than this range, the film blocking will be large, and even if the addition amount exceeds this range, there will be no effect due to the increase in the addition amount and the cost will increase. May cause foaming.

Melt flow rate (hereinafter sometimes abbreviated as "MFR") of a resin composition obtained by adding the above additives to the composition (1). JIS K6760, 190 ° C., load 21
The condition of 60 g) is not particularly limited, but is preferably 0.1 to 10 g / 10 minutes from the viewpoint of film processability.

The method for obtaining the above resin composition is not particularly limited, and each component and each additive are mechanically mixed by a Henschel mixer, a ribbon blender, a V blender or the like, an extruder after mechanical mixing, and a banver. A method of kneading in a molten state by a remixer, a kneader, a hot roll or the like and then pelletizing is adopted, but a method of melt kneading by a single-screw or twin-screw extruder is most preferable from the viewpoint of productivity.

In the film for vapor deposition of the present invention, the above resin composition contains a light stabilizer, an ultraviolet absorber, an organic / inorganic filler, an antistatic agent, a colorant, an organic peroxide within a range that does not impair the effects of the present invention. Materials, lubricants, polymer additives and the like can be added. As the polymer additive, a polyolefin graft-reacted with an unsaturated carboxylic acid such as maleic acid or its anhydride in order to increase the vapor deposition strength, a density for improving the impact resistance of the film 0.905 g
/ Cm ³ or less, the maximum peak temperature (Tm) shown by differential scanning calorimetry is less than 100 ° C, and an ethylene / α-olefin copolymer and the like can be mentioned. Liquid additives such as fatty acids and their derivatives, which are widely used as lubricants and antistatic agents, and plasticizers, among the additives, significantly reduce the vapor deposition strength and the printability of the vapor deposition surface and are therefore preferably not added.

The method for producing the vapor deposition film of the present invention is not particularly limited, and conventionally known methods such as inflation molding and cast molding can be used. Of these, the inflation molding is preferable because it has an excellent balance of mechanical strength in the machine direction and the transverse direction of the film, and since it can be molded at a low temperature, the addition amount of the antioxidant can be limited.

Known methods for increasing the vapor deposition strength can be employed before subjecting the film obtained by the above-mentioned molding to aluminum vapor deposition. Specific examples of these known methods include a method of subjecting the film to a surface treatment such as corona discharge treatment, flame treatment, plasma treatment, and ozone treatment, a substance having a good affinity with a metal, such as a polyester type or a polyurethane type, Examples thereof include a method of applying an epoxy resin or the like to the film. In the case of the above surface treatment, JI after discharge
Wetting index measured by SK6768 is 37 dyn / cm
It is desirable to process as described above, and 39 dyn /
cm or more is particularly preferable.

The method for depositing a metal on the film for vapor deposition of the present invention is not particularly limited, and known means such as electrothermal heating, sputtering, ion plating, and ion beam are used by a batch or continuous vacuum vapor deposition method. However, an oil pump and a diffusion pump can be installed in a continuous vacuum vapor deposition apparatus equipped with a film feeding section, a vapor deposition section, and a winding section (the film feeding section and the winding section can be outside the vapor deposition apparatus). The pressure inside the device is 10-4To
A general method is to reduce the pressure to rr or less, heat a container containing a metal or a filament attached with a metal to dissolve and evaporate the metal, and continuously evaporate vaporized molecules on the film surface and wind the film. The thickness of the vapor deposition layer of the vapor deposition film thus obtained is generally several tens to several hundreds of angstroms from the viewpoint of adhesiveness, durability and economy.

Examples of the metal to be deposited include aluminum, gold, silver, copper, zinc, nickel, chromium, titanium, selenium, germanium and tin.
Aluminum is preferable in terms of economy, luster, safety and the like.

The thickness of the vapor deposition film of the present invention is not particularly limited, and the film obtained by film forming is sampled with a width of 10 mm in the machine direction and autographed at a speed of 50 mm / min in the machine direction of the film. The load at 5% elongation when stretched is appropriately selected so as to have 400 gf / cm or more, but is usually 30 to 100 μm.
Is preferred. The load at this 5% elongation is 400 gf
If it is less than / cm, the film tends to stretch due to the film winding tension during film forming or vapor deposition processing, and wrinkles and lumps are likely to occur on the wound film. Especially in the continuous vacuum vapor deposition method that is widely adopted as a vapor deposition method, as described above, if the film base material is not exactly aligned with the vapor deposition cooling roll, undeposited lines will be generated in the transverse direction of the film, so film processing It is necessary to apply a higher tension than when the film is stretched. Therefore, if the load at 5% elongation is small, the tension cannot be maintained and undeposited lines are likely to occur. Knots are more likely to occur. In order to prevent wrinkles at the time of winding, winding lumps, and unevenness of vapor deposition during vapor deposition due to the reduction of the load at the time of 5% elongation, fatty acid amide, which is most effective as a lubricant, is added in order to impart slip property to the film. When wound by tension, the addition of fatty acid amide deteriorates the vapor deposition strength, the printability of the vapor deposition surface and the suitability for lamination, and no improvement in vapor deposition unevenness is observed.

[0028]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. The performances in Examples and Comparative Examples were measured by the following methods. Further,% in the examples and comparative examples is% by weight, and parts are parts by weight.

Heat-sealing strength A pressure of 2 kgf / c is applied to each film of vapor-deposited films.
The heat-sealing was performed under the conditions of m ² and time of 1 second, and the peel strength when peeled at a peeling speed of 300 mm / min was measured using an autograph. It was evaluated that the low temperature heat sealability was excellent if the heat seal strength was 0.3 kgf / 15 mm or more at 120 ° C.

Vapor Deposition Strength A polyurethane adhesive was applied to the surface of metal vapor deposition at a thickness of ² g / m ² , and a nylon film having a thickness of 15 μm was stuck thereon, followed by aging at 40 ° C. for 48 hours.
Peel strength between nylon film and vapor-deposited film at a speed of 300 mm / min using an autograph (unit: gf / 15 m
m) was measured. Usually, it is peeled off between the vapor deposition substrate film and the vapor deposition layer. It was evaluated that the vapor deposition strength was excellent if it had a vapor deposition strength of 100 gf / 15 mm or more.

Printability and Laminating Suitability of Deposition Surface The deposition surface of a metal deposition film and the film surface are overlapped, and a load of 5 kgf / 25 cm ² is applied, and the mixture is left in an oven at 40 ° C. for 24 hours, and then deposited according to ASTM D523. The surface wetting index (unit: dyn / cm) was measured. The wettability index is required to be 37 dyn / cm or more in order to have good printability and laminating suitability, and a wettability index of 37 or more was evaluated as ◯, and a value of less than 37 was evaluated as x.

Film winding shape A film roll obtained by continuously winding a vapor-deposited film of a constant length is visually observed, and a flat surface having no wrinkles or no lumps is indicated by ○, and a wrinkle or lumps is present. The thing was evaluated as x.

Vapor-deposited appearance Visually observing the vapor-deposited film, the vapor-deposited film is smooth and evenly glossy, and the glossiness measured according to JIS K7105 is 55% or more. It was evaluated as x.

(A) Fine unevenness on the vapor deposition surface (b) Spotless spots without vapor deposition layer, vapor deposition unevenness or darkened vapor deposition surface (c) Glossiness measured according to JIS K7105 5
It is less than 5%. Those evaluated as x have a problem in practical use.

Tear strength The tear strength was measured in accordance with the Elemendorf tear method of JIS K7128.

Tensile Strength and Elongation Measured according to JIS Z1702.

Examples 1 to 3, Comparative Examples 1 to 2 Ethylene / 1-hexene copolymer (density: 0.925 g
/ Cm ³ , MFR; 2 g / 10 min) and low density polyethylene (density; 0.924 g / cm ³ , MFR; 1 g /
Composition (1) 10 containing 10 minutes) in the proportion shown in Table 1
To 0 parts, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (molecular weight; 530.9, trade name; Irganox 1076, Nippon Ciba Geigy (stock) as a phenolic antioxidant )
Manufactured by Tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene phosphonite (trade name; molecular weight: 1035.4, IRG) as a phosphorus-based antioxidant.
AFOS P-EPQ FF, Japan Ciba Geigy Co., Ltd.
Hydrotalcite (trade name; DHT-4A, manufactured by Kyowa Chemical Industry Co., Ltd.) as a catalyst neutralizing agent, and silica (trade name; Shilton PF-) as a blocking inhibitor.
6, Mizusawa Chemical Industry Co., Ltd.) was added in the amounts shown in Table 1, mixed in a tumbler blender, melt-kneaded in a single-screw extruder, and then cooled to pelletize.

Next, using an inflation molding machine composed of an extruder having a diameter of 90 mm and an annular die having a diameter of 450 mm having a slit of 2.8 mm connected to the extruder, melting was carried out under the conditions of a resin temperature of 170 ° C. and a blow ratio of 2.3. After extrusion, air-cooling and corona discharge treatment on one side, then speed 15m /
The winding thickness is 60 μm, and the wettability index of the treated surface is 40 dy.
A tubular film of n / cm was obtained. Table 1 shows the results of measuring the load of the film at 5% elongation in the machine direction.

Next, the obtained film was set in a continuous vacuum vapor deposition apparatus, and aluminum was vapor-deposited on the film under a vacuum of 10-4 Torr or less so that the thickness of the wound vapor deposition film was 45.
0 angstrom width 1500 mm, length 6000 m
A roll-shaped vapor deposition film of was obtained.

Table 1 shows the properties of the obtained vapor-deposited film.

The films of Examples 1 to 3 of the present invention were excellent in the properties that the vapor deposition film should have, such as vapor deposition strength, vapor deposition appearance, and printability of the vapor deposition surface. The vapor-deposited film of Comparative Example 1 in which the load at 5% elongation in the machine direction of the film was less than 400 gf / cm had wrinkles, a poor winding shape, vapor-deposition unevenness, and a vapor-deposited appearance. The vapor deposition film of Comparative Example 2 in which the amount of the phenolic antioxidant added in the resin composition exceeds 0.2 parts and the amount of the adjacent antioxidant added exceeds 0.1 parts has a low vapor deposition strength and a vapor deposition surface. Is inferior in printability and laminating suitability.

Comparative Examples 3 to 4 The same composition ratio as in Example 1 except that the ethylene / 1-hexene copolymer and low density polyethylene having the MFR and density shown in Table 2 were used in the composition (1). In the same manner as in Example 1, the same additives were added to prepare composition pellets, which were subjected to inflation molding and aluminum vapor deposition.

Table 1 shows the load of the film at 5% elongation in the machine direction and the properties of the vapor-deposited film.

The vapor-deposited film of Comparative Example 3 using the ethylene / α-olefin copolymer having a density of less than 0.910 g / cm ^{3 in the} composition (1) had wrinkles and a poor winding appearance. The vapor deposition is uneven and the vapor deposition appearance is poor, and the vapor deposition strength and the printability and laminating suitability of the vapor deposition surface are poor. The vapor-deposited film of Comparative Example 4, which used an ethylene / α-olefin copolymer having a density of more than 0.935 g / cm ³ in the composition (1), was inferior in low-temperature heat sealability.

Comparative Example 5 Instead of the low density polyethylene blended in the composition (1) of Example 1, high density polyethylene (density: 0.953 g /
cm ³ , MFR; 1.0 g / 10 min), except that
Composition pellets were prepared by adding the same additives in the same proportions as in Example 1, prepared by inflation molding in the same manner as in Example 1, and subjected to aluminum vapor deposition. Table 1 shows the load of the film at 5% elongation in the machine direction and the properties of the vapor-deposited film.

This resin composition using high-density polyethylene has poor processing stability, and the film has a rough surface.
The obtained vapor-deposited film has a poor vapor-deposited appearance such as gloss on the vapor-deposited surface and lacks low-temperature heat sealability.

Comparative Example 6 Instead of the phenol-based antioxidant and the adjacent antioxidant blended in the resin composition of Example 1, 2,6-di-t-butyl-4-methylphenol (as a phenol-based antioxidant Molecular weight: 220, trade name; BHT Swanox, manufactured by Yoshitomi Pharmaceutical Co., Ltd., and triphenyl phosphite (molecular weight: 310, trade name; JP-360, as an adjacent antioxidant.
Except for using Johoku Chemical Co., Ltd., composition pellets were prepared by adding the same additives in the same proportions as in Example 1, inflation molding was performed in the same manner as in Example 1, and aluminum vapor deposition was performed. did.

Table 1 shows the load of the film at 5% elongation in the machine direction and the properties of the vapor-deposited film.

The vapor-deposited film using an antioxidant having a molecular weight of less than 500 has many gels and weak vapor deposition strength, and the vapor deposition surface is inferior in printability and laminating suitability and the vapor deposition appearance is poor.

Comparative Example 7 A composition pellet was prepared in the same manner as in Example 1 except that 0.2 part of erucic acid amide was further added to the resin composition of Comparative Example 1, and inflation molding was carried out in the same manner as in Example 1. , Aluminum vapor deposition was performed.

Table 1 shows the load when the film was stretched by 5% in the machine direction and the properties of the vapor-deposited film.

Although the winding shape of the vapor-deposited film containing erucic acid amide was improved, the vapor deposition strength and printability of the vapor deposition surface
Poor laminating suitability and vapor deposition appearance.

Examples 4 to 6 and Comparative Example 8 Compositions in which the components of the composition (1), the density / MFR ethylene / 1-butene copolymer and low density polyethylene shown in Table 2, were blended in the proportions shown in Table 1. For 100 parts,
As a phenolic antioxidant 3,9-bis [2-
[3- (3-t-butyl-4-hydroxy-5
-Methyl phenyl) propionylo
xy] -1,1,1-dimethyl ethyl]-
2,4,8,10-tetraoxaspiro [5,
5] undecane (molecular weight; 741, trade name; Su
milizer GA-80, manufactured by Sumitomo Chemical Co., Ltd., tris (2,4-di-t-butylphenyl) phosphite (molecular weight; 646.9, trade name; IRGAFOS 168, Nippon Ciba Geigy Co., Ltd.) as a phosphorus antioxidant )
Hydrotalcite (trade name; DHT-4A, manufactured by Kyowa Chemical Industry Co., Ltd.) as a catalyst neutralizing agent, and aluminosilicate (trade name; Shilton JC-30, Mizusawa Chemical Industry Co., Ltd.) as a blocking inhibitor. )) Was added in the amount shown in Table 1 to prepare a composition pellet in the same manner as in Example 1,
Inflation molding was performed in the same manner as in Example 1, and aluminum vapor deposition was performed.

Table 1 shows the load of the film at 5% elongation in the machine direction and the properties of the vapor-deposited film.

The vapor deposition films of Examples 4 to 6 have vapor deposition strength,
The vapor deposition film had excellent properties such as appearance and printability of the vapor deposition surface that the vapor deposition film should have. In addition, the vapor deposition film of Comparative Example 8 in which the addition amount of tris (2,4-di-t-butylphenyl) phosphite exceeds 0.05 parts has vapor deposition unevenness and is inferior in vapor deposition appearance.

Comparative Example 9 Composition pellets were prepared in the same manner as in Example 1 except that the proportion of low density polyethylene in the composition (1) was changed to 50% by using the same components and additives as in Example 1. Inflation molding was performed in the same manner as in Example 1. Table 3 shows the results of measuring the tear strength, tensile strength and elongation of this film and the inflation-molded film of Example 1.
The film of Comparative Example 9 in which the proportion of low density polyethylene in the composition (1) exceeds 40% is inferior in tear strength, tensile strength and elongation.

[0057]

[Table 1]

[0058]

[Table 2]

[0059]

[Table 3]

[0060]

Since the polyethylene film for metal vapor deposition of the present invention has a low temperature heat-sealing property, it can be suitably used as a packaging material by itself without subjecting the film to a top coat or laminating after vapor deposition. However, taking advantage of the excellent printability and laminating suitability of the vapor deposition surface, printing and topcoating on the vapor deposition surface,
Anchor coat is applied to the vapor-deposited surface and a resin such as polyolefin, polyester, nylon, and Eval is laminated on the vapor-deposited surface, and heat-sealed with the films as inner surfaces to obtain a highly functional package.

[Brief description of drawings]

FIG. 1 is a schematic view of a continuous vacuum vapor deposition apparatus.

[Explanation of symbols]

1; Unwinding shaft, 2; Cooling roll, 3; Evaporation source, 4; Winding shaft

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] August 3, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction content]

The method for depositing a metal on the film for vapor deposition of the present invention is not particularly limited, and known means such as electrothermal heating, sputtering, ion plating, and ion beam are used by a batch or continuous vacuum vapor deposition method. However, an oil pump and a diffusion pump can be installed in a continuous vacuum vapor deposition apparatus equipped with a film feeding section, a vapor deposition section, and a winding section (the film feeding section and the winding section can be outside the vapor deposition apparatus). The pressure inside the device is 10 ^-4 Tor
In general, the pressure is reduced to r or less, the container containing the metal or the filament to which the metal is attached is heated to dissolve and evaporate the metal, and vaporized molecules are continuously deposited on the film surface and wound up. The thickness of the vapor deposition layer of the vapor deposition film thus obtained is generally several tens to several hundreds of angstroms from the viewpoint of adhesiveness, durability and economy.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0039

[Correction method] Change

[Correction content]

Next, the obtained film was set in a continuous vacuum vapor deposition apparatus, and aluminum was vapor-deposited on the film under a vacuum of 10 ^-4 Torr or less, and the thickness of the wound vapor deposition film was 450.
A roll-shaped vapor deposition film having an angstrom width of 1500 mm and a length of 6000 m was obtained. ─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] August 31, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction content]

Examples of the metal to be deposited include aluminum, gold, silver, copper, zinc, nickel, chromium, titanium, selenium, germanium and tin.
Aluminum is preferable in terms of economy, luster, safety and the like. ─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] September 2, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction content]

The α-olefin which is a comonomer of the ethylene / α-olefin copolymer used as a component of the composition (1) in the film for vapor deposition of the present invention has the general formula R-CH = CH ₂ (wherein R is Represents an alkyl group having 1 to 14 carbon atoms, and specific examples thereof include propylene, 1-butene, 1-hexene, 1-decene, 1-octene and 4-methyl-1-. Pentene, 1-nonene, 4-methyl-1-hexene and the like can be mentioned. The comonomer content is not particularly limited, but is 0.1
-10 mol% is preferable.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0025

[Correction method] Change

[Correction content]

The method for depositing a metal on the film for vapor deposition of the present invention is not particularly limited, and known means such as electrothermal heating, sputtering, ion plating, and ion beam are used by a batch or continuous vacuum vapor deposition method. However, an oil pump and a diffusion pump can be installed in a continuous vacuum vapor deposition apparatus equipped with a film feeding section, a vapor deposition section, and a winding section (the film feeding section and the winding section can be outside the vapor deposition apparatus). The pressure inside the device is 10 ^-4 Tor
In general, the pressure is reduced to r or less, the container containing the metal or the filament to which the metal is attached is heated to dissolve and evaporate the metal, and vaporized molecules are continuously deposited on the film surface and wound up. The thickness of the vapor deposition layer of the vapor deposition film thus obtained is generally several tens to several hundreds of angstroms from the viewpoint of adhesiveness, durability and economy.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0039

[Correction method] Change

[Correction content]

Next, the obtained film was set in a continuous vacuum vapor deposition apparatus, and aluminum was vapor-deposited on the film under a vacuum of 10 ^-4 Torr or less, and the thickness of the wound vapor deposition film was 450.
A roll-shaped vapor deposition film having an angstrom width of 1500 mm and a length of 6000 m was obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display area C08L 23/04 LCD

Claims (2)

[Claims] 1. A low-density polyethylene having a density of 0.910 to 0.935 g / cm ³ of a copolymer of ethylene and α- olefin 60-95 wt% and density 0.910~0.940g / cm ³ 5 -40% by weight of the composition (1) 1
0.01 to 0.2 parts by weight of a phenolic antioxidant having a molecular weight of 500 or more, and a molecular weight of 500 to 100 parts by weight.
0.01 to 0.1 part by weight of the above phosphorus-based antioxidant, 0.01 to 0.1 part by weight of hydrotalcite, and 0.05 to 0.5 part by weight of an antiblocking agent are added,
A polyethylene film for metal vapor deposition having a load of 400 gf / cm or more at 5% elongation in the machine direction. 2. Tris (2,4-) as an adjoining antioxidant having a molecular weight of 500 or more per 100 parts by weight of composition (1).
Di-t-butylphenyl) phosphite 0.01-
The polyethylene film for metal vapor deposition according to claim 1, wherein 0.05 part by weight is added.