JPH0747638A - Metallized multilayered film - Google Patents

Abstract

PURPOSE:To enhance low temp. sealability, the bonding strength of a vapor deposition film and the printability to a vapore deposition surface by using a two-layered film based on an ethylene/alpha-olefin copolymer resin limited in the kinds and amts. of additives and different in density as a vapor deposition base material. CONSTITUTION:A multilayered film has a first layer constituted of a compsn. A consisting of an ethylene/a-olefin copolymer with density of 0.910-0.929 g/cm<3> and low density polyethylene with density of 0.910-0.940 g/cm<3> and a resin compsn. B containing a phenolic oxidation inhibitor with a mol. wt. of 500 or more and a phosphoric oxidation inhibitor with a mol. wt. of 500 or more, a second layer constituted of a compsn. C consisting of an ethylene/a-olefin copolymer with density of 0.930-0.940g/cm<3> and low density polyethylene with density of 0.910-0.940g/cm<3> and a compsn. D containing a phenolic oxidation inhibitor with a mol. wt. of 500 or more and a phosphoric oxidation inhibitor and a third metal vapor deposited layer.

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 metal vapor-deposited multi-layer film having a good vapor-deposition appearance without a winding defect such as "rolled hump".

[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, it is also necessary to have an excellent vapor deposition appearance, such as having a uniform gloss without vapor deposition unevenness.

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 film during storage in the wound state of the vapor deposition film. It is described that it is due to the transfer of the additive therein 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, in JP-A-59-25829, a composition of 80 to 96% by weight of a propylene / α-olefin copolymer having a specific melt flow rate ratio and 4 to 20% by weight of high density polyethylene is further added. As the agent, 0.01 to 0.3% by weight of a phenol-based or phosphorus-based antioxidant having a molecular weight of 500 or more, and 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 description relates 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. A method for producing a 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 not been proposed so far.

[0005]

The objects of the present invention are low temperature heat sealability, adhesive strength of vapor deposition film, printability on vapor deposition surface,
A metal-deposited multi-layer ethylene / α-olefin that has excellent laminating suitability, does not have winding defects such as "wrinkles" and "rolled humps" during film winding during film forming and vapor deposition processing, and has excellent vapor deposition appearance such as gloss. It is to provide a copolymer film.

[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, it is difficult to solve all of the problems by using a monolayer film as a vapor deposition substrate, and a two-layer structure in which ethylene / α-olefin copolymers having different densities with limited types and amounts of additives are used as a base resin. It was found that all of the above problems can be solved by using a film as a vapor deposition substrate, and the present invention has been completed.

That is, the present invention is (A) / (B) / (C) 3
It is a laminate having a layer structure, and the layer (A) has a density of 0.910 to 1010.
Copolymer of 0.929 g / cm ³ of ethylene and α-olefin 60 to 95% by weight and density of 0.910 to 0.9
A composition having a molecular weight of 5 is added to 100 parts by weight of a composition (1) consisting of 5 to 40% by weight of 40 g / cm ³ of low-density polyethylene.
0.01 to 0.2 of a phenolic antioxidant of 00 or more
By weight, a phosphorus-based antioxidant having a molecular weight of 500 or more is added to 0.0
1-0.1 parts by weight, hydrotalcite 0.01-0.
1 part by weight and anti-blocking agent 0.05-0.5
The resin composition (3) is added with parts by weight, and the layer (B) has a density of 0.930 to 0.940 g / cm ^{3 and} a copolymer of ethylene and α-olefin of 60 to 95% by weight and a density of 0. 0.01 to 0.2 parts by weight of a phenolic antioxidant having a molecular weight of 500 or more per 100 parts by weight of a composition (2) consisting of 5 to 40% by weight of low density polyethylene of 910 to 0.940 g / cm ^3. A resin composition (4) containing 0.01 to 0.1 part by weight of a phosphorus-based antioxidant having a molecular weight of 500 or more and 0.01 to 0.1 part by weight of hydrotalcite, (A) / (B) The load at the time of 5% elongation of the two-layer film in the machine direction is 400 gf / cm or more,
The (C) layer is a metal vapor-deposited multilayer film, which is a metal vapor deposition layer.

The present invention will be described in detail below.

The low density polyethylene used as a component of the composition (1) and the composition (2) in the metal vapor-deposited multilayer film of the present invention is blended for the purpose of improving the processability of the ethylene / α-olefin copolymer. It is a homopolymer of ethylene produced by a high pressure method having a density of 0.910 to 0.940 g / cm ³ , preferably 0.915 to 0.930 g / cm ³ . It is difficult to industrially produce a product having a density outside this range by the high pressure method.
The density is 0.940 g / cm instead of low density polyethylene
^When a high-density polyethylene exceeding ³ is used, the film processability deteriorates, and in the composition (1), the unevenness of the film surface becomes severe, resulting in a decrease in the gloss of the vapor deposition surface and a deterioration of the low-temperature heat-sealing property, and a packaging material. Is not preferable because it lacks high-speed productivity.

The α-olefin which is a comonomer of the ethylene / α-olefin copolymer used as a component of the composition (1) and the composition (2) in the metal vapor-deposited multilayer film of the present invention is represented by the general formula R-CH. = CH ₂ (wherein R
Represents an alkyl group having 3 to 16 carbon atoms. ), Propylene, 1-butene, 1
-Hexene, 1-decene, 1-octene, 4-methyl-
1-Pentene, 1-nonene, 4-methyl-1-hexene and the like can be mentioned. The content of such comonomer is not particularly limited, but is preferably 0.1 to 10 mol%.

The ethylene / α-olefin copolymer used as a component of the composition (1) in the vapor-deposited multilayer film of the present invention has a density (JIS K6760) of 0.
910 to 0.929 g / cm ³ , preferably 0.915
Is about 0.927 g / cm ³ . When the density of the copolymer is less than 0.910 g / cm ³ , the low molecular weight component in the copolymer increases, resulting in lack of blocking resistance (A) /
(B) The vapor deposition strength is lowered due to the transfer of the low molecular weight component to the surface of the layer (B) in the wound state of the two-layer film, and to the vapor deposition surface due to the transfer of the low molecular weight component to the vapor deposition surface in the wound state of the vapor deposited film. Printability and laminating suitability are deteriorated. Furthermore, as a result of lowering the rigidity 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 which is widely adopted as the vapor deposition method, an undeposited line (rail) is formed in the transverse direction of the film unless the film base material is exactly aligned with the vapor deposition cooling roll 2 shown in FIG.
Therefore, it is necessary to apply a higher tension than when processing the film.Therefore, if the rigidity of the film decreases, the tension cannot be maintained and undeposited lines are likely to occur. Wrinkles and lumps are more likely to occur. In order to prevent wrinkles at the time of winding due to such a decrease in film rigidity, lumps and unevenness in vapor deposition during vapor deposition, fatty acid amide, which is most effective as a lubricant to impart slip properties to the film, is added and wound with low tension. If taken, 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 0.929 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 ethylene / α-olefin copolymer used as a component of the composition (2) in the metal vapor-deposited multilayer film of the present invention has a density (JIS K6760) of 0.930 to 0.940 g / cm ³ , preferably Is 0.9
It is 32-0.937 g / cm ³ . When the density of the copolymer is less than 0.930 g / cm ³ , heat resistance is poor, and
The radiant heat of the molten metal causes wrinkles in the film that comes into contact with the vapor deposition cooling roll, which is relatively high in temperature, which causes vapor deposition unevenness and reduces vapor deposition strength. If the density of the copolymer exceeds 0.940 g / cm ³ , its industrial production becomes difficult.

The mixing ratio of the ethylene / α-olefin copolymer in the composition (1) and the composition (2) is 6 in both cases.
It is 0 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, etc., which are characteristic of the ethylene / α-olefin copolymer film, is lowered, and the heat seal strength is lowered in the composition (1). Further, if it exceeds this range, the workability is deteriorated.

In the metal vapor-deposited multilayer film of the present invention, the type of the additive added to the composition (1) and the composition (2) is not limited, or even if the type is limited, if the addition amount is too large, the vapor deposition strength is increased. And the printability and laminating suitability of the vapor deposition surface 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.

In the metal vapor-deposited multilayer film of the present invention, the molecular weight added to the composition (1) and the composition (2) is 5
As a phenolic antioxidant of 00 or more, monophenolic, bisphenolic, thiobisphenolic,
Examples thereof include trisphenol-based antioxidants, and more specific examples include 2,4-bis- (n-octylthio).
-6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine (commercially available from Nippon Ciba Geigy Co., Ltd. under the trade name Irganox 565), 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 (eg Nippon Ciba Geigy Co., Ltd. ) From the product name Irganox 107
6 is commercially available. ), 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 (for example, Irganox 31 from Japan Ciba Geigy Co., Ltd.)
It is marketed as 14. ), 1,1,3-tris-
(2-Methyl-4-hydroxy-5-t-butylphenyl) butane (commercially available under the trade name MARKAO-30 from Adeka Argus Chemical Co., Ltd.), tris- (4-t-butyl-2,2). 6-di-methyl-3-hydroxybenzyl) isocyanurate (eg Am. C
Product name Cyanox1790 from yanamid Co., Ltd.
Is marketed as. ), 1,3,5-trimethyl-
2,4,6-Tris- (3,5-di-t-butyl-4-
Hydroxybenzyl) benzene (commercially available from Shiraishi Calcium Co., Ltd. under the trade name SEENOX 326M), 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-but.
yl-4-hydroxy-5-methyl phe
nyl) propionyloxy] -1,1, dim
Ethyl]]-2,4,8,10-tet
raoxaspiro [5,5] undecane (eg Sumilizer G from Sumitomo Chemical Co., Ltd.)
It is commercially available as A-80. ) And the like, which are used alone or as a mixture of two or more kinds.
Among the above phenolic antioxidants, octadecyl-3
Most preferred is-(3,5-di-t-butyl-4-hydroxyphenyl) propionate (commercially available from Nippon Ciba Geigy Co., Ltd. under the trade name Irganox 1076).

In the metal vapor-deposited multilayer film of the present invention, the molecular weight added to the composition (1) and the composition (2) is 5 or less.
Specific examples of the phosphorus-based antioxidants of 00 or more include tris (2,4-di-t-butylphenyl) phosphite (trade name IRGAF from Nippon Ciba-Geigy Co., Ltd.).
It is commercially available as OS168. ), 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), Tris. (Nonylphenyl) phosphite (commercially available, for example, from ADEKA ARGUS CHEMICAL CO., LTD. Under the trade name MARK 1178), distearyl pentaerythritol-di-phosphite (for example, ADEKA ARGUS CHEMICAL CO., LTD., Trade name MARK).
It is commercially available as PEP-8. ), Di (2,4-
Di-t-butylphenyl) -pentaerythritol-di-phosphite (commercially available under the trade name MARK PEP-24 from Adeka Argus Chemical Co., Ltd.), di (nonylphenyl) pentaerythritol-
Di-Phosphite (eg ADEKA ARGUS CHEMICAL CO., LTD.
Marketed under the trade name MARK PEP-4C. ), Phenyl-bisphenol A pentaerythritol-di-phosphite (commercially available under the trade name MARK PEP-2 from Adeka Argus Chemical Co., Ltd.), sodium bis (4-t-butylphenyl) phosphate (e.g. Adeca). Argus Chemical Co., Ltd.
Marketed under the trade name MARKNA-10. ), Bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite (commercially available from Adeka Argus Chemical Co., Ltd. under the trade name ADEKA STAB PEP-36) and the like. And used alone or as a mixture thereof. Among the above phosphorus-based antioxidants, tris (2,4-di-t-butylphenyl) phosphite (commercially available from Nippon Ciba Geigy Co., Ltd. under the trade name IRGAFOS168) and tetrakis (2,4-di-). t-butylphenyl) -4,4'-biphenylene phosphonite (trade name IRGAFOS from Nippon Ciba Geigy KK)
It is commercially available as P-EPQ FF. ) Is most preferred.

The amount of the above antioxidant added is 0.01 to 0.2 parts by weight, preferably 0.05 to 0. 0, parts by weight of the phenolic antioxidant per 100 parts by weight of the composition (1) or (2).
1 part by weight, 0.01 to 0.1, preferably 0.05 to 0.09 parts by weight of the phosphorus-based antioxidant. 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, printability of the vapor deposition surface, and laminating suitability deteriorate. In addition, an antioxidant having a molecular weight of less than 500 easily volatilizes due to heat during film forming and vapor deposition and is inferior in the development of antioxidative ability, and the vapor deposition appearance deteriorates due to bleed-out, and the vapor deposition strength and printability of the vapor deposition surface Aptitude decreases. The above-mentioned antioxidants are required to be used in combination with phenol-based and phosphorus-based, and by using them together, the antioxidant ability is improved and the total amount of antioxidants is suppressed to suppress vapor deposition strength and printability of the vapor deposition surface / laminate. It is possible to prevent deterioration of suitability. When tris (2,4-di-t-butylphenyl) phosphite is used as the phosphorus-based antioxidant, the addition amount thereof is particularly limited and is 0.01-
0.05 parts by weight is preferred. If the amount added exceeds 0.05 part by weight, bleed-out becomes severe depending on the film processing conditions and the like, which causes unevenness in vapor deposition and a decrease in vapor deposition strength, which is not preferable.

The hydrotalcite added to the composition (1) and the composition (2) in the metal vapor-deposited multilayer film of the present invention means 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⁺ , N
i ²⁺ , Cu ²⁺ , Zn ^2+, etc., a divalent metal, L is Al ³⁺ ,
Fe ³⁺ , Cr ³⁺ , Co ³⁺ , In ³⁺
Is OH ⁻ , F ⁻ , Cl ⁻ , Br ⁻ , NO ₃ ⁻ , CO ₃ ²⁻ , SO ₄
^2- , Fe (CN) ₆ ³⁻ , CH ₃ COO ⁻ , n-valent anions such as oxalate ion and salicylate ion, and x is 0 <
The number in the range of x ≦ 0.33 is shown. ), And is used as a neutralizing agent for the acidic substance of the catalyst residue in the ethylene / α-olefin copolymer in the compositions (1) and (2), and is exemplified by Mg ₆ Al. ₂ (OH) ₁₆ CO
Natural mineral having a composition of _{3 · 4H 2 O, Mg 4.5} Al 2 (O
H) Synthetic hydrotalcite having a composition of ₁₃ CO ₃ .3.5H ₂ O (for example, trade name DH from Kyowa Chemical Industry Co., Ltd.)
It is commercially available as T-4A. ) Etc. can be mentioned.

The amount of the above-mentioned hydrotalcite added is 0.01 to 0. 0 based on 100 parts by weight of the composition (1) or (2).
It is 1 part by weight, preferably 0.02 to 0.06 part by weight. 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 antiblocking agent added to the composition (1) in the metal vapor-deposited multilayer film of the present invention include kaolins such as kaolinite, decalite, nacrite, halloysite, hydrohalloysite, and allophane, aluminosilicates. And natural and synthetic zeolites and derivatives thereof, silicon oxide, aluminum oxide, calcium carbonate, barium sulfate and the like.

The antiblocking agent is added in an amount of 0.05 to 0.5 parts by weight, preferably 0.1 to 0.4 parts by weight, based on 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.

Resin composition (3) containing the above additives
The melt flow rate of (4) (hereinafter sometimes abbreviated as "MFR"; conditions of JIS K6760, 190 ° C., load 2160 g) is not particularly limited, but 0.1 to 10 g from the viewpoint of film processability. / 10 minutes is preferable.

The method for obtaining the above resin composition (3) or (4) 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. A method of kneading in a molten state with an extruder, a Banbury mixer, a kneader, a heat roll, etc. and then pelletizing is adopted, but the method of melt kneading with a single-screw or twin-screw extruder is the most in view of productivity. It is suitable.

In the metal vapor-deposited multilayer film of the present invention, the resin composition (3) and the resin composition (4) contain a light stabilizer, an ultraviolet absorber, an organic / inorganic filler, within a range that does not impair the effects of the present invention. Antistatic agents, colorants, organic peroxides, 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 of 0.905 g / cm ³ or less for improving the impact resistance of the film, An ethylene / α-olefin copolymer having a maximum peak temperature (Tm) shown by differential scanning calorimetry of less than 100 ° C. can be mentioned. Among the additives, liquid additives such as fatty acids and their derivatives, which are widely used as lubricants and antistatic agents, and plasticizers significantly reduce the vapor deposition strength and the printability of the vapor deposition surface, so it is preferable not to add them. The method for producing the (A) / (B) two-layer film in the metal vapor-deposited multilayer film of the present invention is not particularly limited, and may be based on the coextrusion inflation method, the coextrusion casting method, (A) or (B). A conventionally known method such as a method of extruding and laminating the resin composition (4) or (3) as a material and a method of dry laminating the films of (A) and (B) are adopted. Among the above methods, the coextrusion method is preferable from the viewpoint of productivity, good balance between the mechanical strength of the film in the machine direction and the transverse direction, and because it can be molded at a low temperature, the addition amount of the antioxidant can be suppressed. The coextrusion inflation molding method is more preferable.

A publicly known method for increasing the vapor deposition strength before aluminum vapor deposition on the (B) layer side of the two-layer film obtained by the above-mentioned molding method can be adopted. Specific examples of these known methods include a method of subjecting the layer (B) to surface treatment such as corona discharge treatment, flame treatment, plasma treatment, ozone treatment, and the like, substances having a good affinity with metals such as polyester and polyurethane. Examples of the method include applying a resin or epoxy resin to the layer (B). In the case of the above surface treatment, it is desirable that the surface treatment is such that the wetting index measured by JIS K6768 after discharge is 37 dyn / cm or more, and particularly preferably 39 dyn / cm or more.

The method of vapor depositing a metal in the vapor-deposited multilayer film 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. It is possible, but the film feeding part, vapor deposition part,
In a continuous vacuum vapor deposition apparatus equipped with a winding section (the film feeding section and the winding section may be outside the vapor deposition apparatus), an oil pressure and a diffusion pump are used together to reduce the atmospheric pressure in the apparatus to 10
^It is a general method to reduce the pressure to ^-4 Torr or less, heat a container containing a metal or a filament to which a metal is attached to dissolve and evaporate the metal, and continuously evaporate vaporized molecules on the film surface and wind the film. The thickness of the vapor-deposited layer of the vapor-deposited film thus obtained is generally tens to hundreds of angstroms from the viewpoint of adhesiveness, durability and economy.

The metal to be vapor-deposited includes, for example, 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 each layer of (A) and (B) in the vapor-deposited multilayer film of the present invention is not particularly limited, and the (A) / (B) two-layer film is 10 mm in the machine direction.
It is appropriately selected so that the load at 5% elongation when sampled by the width and stretched at a speed of 50 mm / min in the machine direction of the film by an autograph has 400 gf / cm or more, but usually (A) / ( B) Layer thickness is 30-100μ
The thickness of each layer of m, (A), and (B) is preferably 5 to 95 μm. When the load at the time of 5% elongation is less than 400 gf / cm, the multilayer film is easily stretched due to the film winding tension at the time of coextrusion processing or vapor deposition processing, and wrinkles or lumps easily occur on the winding 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 and lumps at the time of winding due to the reduction of the load at the time of 5% elongation and unevenness of vapor deposition at the time of vapor deposition, fatty acid amide most effective as a lubricant is added to impart slip property to the film. When wound with low 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 the vapor deposition unevenness is not improved.

[0029]

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-seal strength Pressure (2kgf / cm) between layers (B) of metallized film
² , the heat-sealing was performed under the condition of 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 multilayer vapor-deposited film at a speed of 300 mm / min using an autograph (unit: gf / 1
5 mm) was measured. Usually, it is peeled off between the (B) layer 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 the metal deposition multi-layer film and the (A) layer surface are overlapped and a load of 5 kgf / 25 cm ² is applied and left in an oven at 40 ° C. for 24 hours, and then ASTM D523 is applied. According to this, the wetting index (unit: dyn / cm) of the vapor deposition surface 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 and Comparative Examples 1 to 3 As the resin composition (3) for the layer (A), an ethylene / 1-hexene copolymer (density: 0.925 g / cm ³ , MF
R; 2 g / 10 min) and low density polyethylene (density;
0.924 g / cm ³ , MFR; 1 g / 10 minutes)
Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (molecular weight: 530.9, trade name; Irganox 10
76, manufactured by Nippon Ciba-Geigy Co., Ltd., tetrakis (2,4-di-t-butylphenyl) as a phosphorus-based antioxidant.
-4,4'-Biphenylene phosphonite (trade name;
Molecular weight: 1035.4, IRGAFOS P-EPQ
FF, manufactured by Ciba-Geigy Co., Ltd., hydrotalcite (trade name; DHT-4A, manufactured by Kyowa Chemical Industry Co., Ltd.) as a catalyst neutralizer, and silica (trade name; Shilton PF-6) as an anti-blocking agent. , Mizusawa Chemical Industry Co., Ltd.)
Was added in an amount shown in Table 1, mixed with a tumbler blender, melt-kneaded with a single-screw extruder, cooled, and pelletized.
Further, as the resin composition (4) for the layer (B), ethylene / 1
-Hexene copolymer (density; 0.935 g / cm ³ , M
FR; 2 g / 10 min) and low-density polyethylene (density: 0.924 g / cm ³ , MFR; 1 g / 10 min) were mixed at a ratio shown in Table 1 to 100 parts of the composition as a phenolic antioxidant. Octadecyl-3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate (trade name; Irganox 1076, manufactured by Ciba-Geigy Co., Ltd.), tetrakis (2,4-di-t-butylphenyl) -as a phosphorus antioxidant. 4,4'-biphenylene phosphonite (trade name; IRGAFOS
P-EPQ FF, manufactured by Ciba-Geigy Co., Ltd., is used as a catalyst neutralizing agent in hydrotalcite (trade name; DHT-).
4A, manufactured by Kyowa Chemical Industry Co., Ltd.) in an amount shown in Table 1,
After mixing with a tumbler blender, they were melt-kneaded with a single-screw extruder, cooled, and pelletized.

Next, using a coextrusion inflation molding machine consisting of two extruders and an annular two-layer die having a diameter of 450 mm and having a slit of 2.8 mm connected thereto, one of the extruders having a diameter of 75 mm was made to have a resin composition. Thing (3)
And the resin composition (4) was fed to the other extruder having a diameter of 75 mm, and the resin temperature was 170 ° C. for both (3) and (4).
After being laminated in a molten state in a two-layer die connected by, air-cooled inflation molding was performed under the condition of a blow ratio of 2.3, the surface of the (B) layer was subjected to corona discharge treatment, and then wound at a speed of 15 m / min. A tubular two-layer film having each layer thickness shown in was obtained.
The results of measuring the load of 5% elongation in the machine direction of the two-layer film are shown in Table 1.

Next, the obtained film was set in a continuous vacuum vapor deposition apparatus and aluminum was vapor-deposited on the layer surface (B) of the two-layer film under a vacuum of 10 ^-4 Torr or less, and the film was wound up to a thickness of 450. Angstrom width 1500 m
A roll-shaped vapor deposition film having a length of m and a length of 6000 m was obtained.

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

The multilayer vapor-deposited films of Examples 1 to 3 obtained according to the present invention were excellent in properties that the vapor-deposited film should have, such as vapor deposition strength, vapor deposition appearance, and printability of the vapor deposition surface. (A)
/ (B) The vapor-deposited film of Comparative Example 1 in which the load at 5% elongation in the machine direction of the bilayer film was less than 400 gf / cm had wrinkles, a poor winding appearance, vapor deposition unevenness, and a vapor deposition appearance was also poor. The vapor-deposited film and resin composition of Comparative Example 2 in which the addition amount of the phenol-based antioxidant in the resin composition (3) exceeds 0.2 part and the addition amount of the adjacent antioxidant exceeds 0.1 part. The addition amount of the phenolic antioxidant in 4) was 0.4.
The vapor deposition film of Comparative Example 3 in which the amount of the adjacent antioxidant exceeds 0.1 part and exceeds 2 parts is inferior in vapor deposition strength, printability of the vapor deposition surface, and laminating suitability.

Comparative Examples 4 to 6 Comparative Examples 4 to 6 were carried out except that the ethylene / 1-hexene copolymer and low density polyethylene shown in Table 2 were used in the compositions (1) and (2). The same additives as in Example 1 were added in the same proportions as in Example 1 to prepare composition pellets, which were subjected to coextrusion inflation molding in the same manner as in Example 1 and aluminum vapor deposition was carried out in the same manner as in Example 1.

Table 1 shows the load of the (A) / (B) bilayer film at 5% elongation in the machine direction and the properties of the vapor-deposited film.

The vapor-deposited film of Comparative Example 4, in which the ethylene / α-olefin copolymer having a density of less than 0.910 g / cm ³ was used in the composition (1), wrinkles occurred and the winding shape was poor. Vapor deposition is uneven and the vapor deposition appearance is poor and the vapor deposition strength is poor, and the printability and laminating suitability of the vapor deposition surface are poor. The vapor-deposited film of Comparative Example 5, which uses an ethylene / α-olefin copolymer having a density of more than 0.929 g / cm ³ in the composition (1), has poor low-temperature heat sealability.
The vapor-deposited film of Comparative Example 6 in which the ethylene / α-olefin copolymer in the composition (2) having a density of less than 0.930 g / cm ³ had vapor deposition unevenness and was poor in vapor deposition strength.

Comparative Example 7 High density polyethylene (density: 0.953 g / cm ³ , MFR: 1 g / instead of the low density polyethylene blended in the resin composition (3) and the resin composition (4) of Example 1) 1
(0 minutes), except that the same additives as in Example 1 were added in the same proportions as in Example 1 to prepare composition pellets, and co-extrusion inflation molding was performed in the same manner as in Example 1. Aluminum vapor deposition was performed as in 1.

Table 1 shows the load of the (A) / (B) bilayer film at 5% elongation in the machine direction and the properties of the vapor-deposited film.

Both the resin compositions (3) and (4) using high-density polyethylene have poor processing stability (A) / (B).
The two-layer film has a rough surface, and the vapor-deposited film obtained has poor gloss on the vapor-deposited surface and lacks low-temperature heat sealability.

Comparative Example 8 Instead of the phenol-based and adjacent-type antioxidants contained in the resin composition (3) and the resin composition (4) of Example 1, 2,6-diphenol was used as a phenol-based antioxidant. -T-Butyl-4-methylphenol (molecular weight; 220, trade name; BHT Swanox, manufactured by Yoshitomi Pharmaceutical Co., Ltd.) was used as triphenyl phosphite (molecular weight; 310, trade name; JP-360) as an adjacent antioxidant. , Johoku Chemical Co., Ltd.
Manufactured by the same method as described in Example 1 except that the composition pellets were prepared.
Co-extrusion inflation molding was carried out as in Example 1, and aluminum vapor deposition was carried out as in Example 1.

Table 1 shows the load of the (A) / (B) bilayer 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 low vapor deposition strength, poor printability and laminating suitability on the vapor deposition surface, and poor vapor deposition appearance.

Comparative Example 9 Comparative Example 5 except that 0.2 parts of erucic acid amide was further added to each of the resin compositions (3) and (4) of Comparative Example 1.
In the same manner as in Comparative Example 5, a composition pellet was prepared, co-extrusion and inflation molding were performed, and aluminum vapor deposition was performed in the same manner as in Comparative Example 5.

Table 1 shows the load of the (A) / (B) bilayer film at 5% elongation in the machine direction and the properties of the vapor-deposited film.

Although the winding appearance 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 10 Density and MFR of Table 2 as components of the compositions (1) and (2)
With respect to 100 parts of a composition in which an ethylene / 1-butene copolymer having 1 to 3 and a low-density polyethylene were blended at a ratio shown in Table 1, 3,9-bis was used as a phenol-based antioxidant.
[2- [3- (3-t-butyl-4-hydrox
y-5-methyl phenyl) propion
[yloxy] -1,1-dimethyl ethyl
l] -2,4,8,10-tetraoxaspiro
[5,5] undecane (molecular weight; 741, trade name; Sumilizer GA-80, Sumitomo Chemical Co., Ltd.)
Manufactured), and tris (2,4-di-t-) as a phosphorus-based antioxidant.
Butylphenyl) phosphite (molecular weight; 646.
9, trade name: IRGAFOS 168, manufactured by Ciba-Geigy Co., Ltd., and hydrotalcite (trade name: DHT-4A, manufactured by Kyowa Chemical Industry Co., Ltd.) as a catalyst neutralizing agent,
As an anti-blocking agent, aluminosilicate (trade name; Shilton JC-30, manufactured by Mizusawa Chemical Industry Co., Ltd.) was added in an amount shown in Table 1 to prepare a composition pellet in the same manner as in Example 1, and the same as in Example 1. Was co-extruded and inflation-molded, and aluminum vapor deposition was performed in the same manner as in Example 1.

Table 1 shows the load of the (A) / (B) bilayer film at 5% elongation in the machine direction and the properties of the vapor-deposited film.

The vapor-deposited films of Examples 4 to 6 obtained according to the present invention were excellent in properties that the vapor-deposited film should have, such as vapor-deposition strength, vapor-deposition appearance, and printability of the vapor-deposited surface. The vapor-deposited film of Comparative Example 10 in which the addition amount of tris (2,4-di-t-butylphenyl) phosphite exceeds 0.05 parts causes vapor deposition unevenness and is inferior in vapor deposition appearance.

Comparative Example 11 Using the same components and additives as in Example 1, the ratio of low density polyethylene in the compositions (1) and (2) was adjusted to 5%.
Composition pellets were produced in the same manner as in Example 1 except that the content was 0%, and coextrusion and inflation molding were 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. Comparative Example 11 in which the proportion of low-density polyethylene in the compositions (1) and (2) exceeds 40%
Film is inferior in tear strength, tensile strength and elongation.

[0058]

[Table 1]

[0059]

[Table 2]

[0060]

[Table 3]

[0061]

The metal-deposited multilayer film obtained by the production method of the present invention has a low-temperature heat-sealing property of the (A) layer. Although it is preferably used as a packaging material by itself without applying it, printing or topcoat is applied to the vapor deposition surface, or polyolefin after anchor coating is applied to the vapor deposition surface by taking advantage of the excellent printability of the vapor deposition surface and the suitability for lamination. By laminating a resin such as polyester, nylon, eval, etc. and heat-sealing the layers (A) with each other as the inner surface, it can be suitably used as a high-performance 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] 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) and the composition (2) in the metal vapor-deposited multilayer film of the present invention is represented by the general formula R-CH. = CH ₂ (wherein R
Represents an alkyl group having 1 to 14 carbon atoms. ), Propylene, 1-butene, 1
-Hexene, 1-decene, 1-octene, 4-methyl-
1-Pentene, 1-nonene, 4-methyl-1-hexene and the like can be mentioned. The content of such comonomer is not particularly limited, but is preferably 0.1 to 10 mol%.

Claims (2)

[Claims] 1. A laminate having a three-layer structure of (A) / (B) / (C), wherein the (A) layer has a density of 0.910 to 0.929 g / c.
Copolymer of m ³ of ethylene and α-olefin 60 to 9
5% by weight and 5 to 40% by weight of a low-density polyethylene having a density of 0.910 to 0.940 g / cm ³ (1) 100 parts by weight of a phenolic antioxidant having a molecular weight of 500 or more. 01-0.2 parts by weight, 0.01-0.1 parts by weight of a phosphorus-based antioxidant having a molecular weight of 500 or more, 0.01-0.1 parts by weight of hydrotalcite, and 0.05-part of an anti-blocking agent. The resin composition (3) containing 0.5 parts by weight of (B) has a density of 0.93.
Copolymer of ethylene and α-olefin of 0 to 0.940 g / cm ³ 60 to 95% by weight and density of 0.910
A phenolic antioxidant having a molecular weight of 500 or more is added in an amount of 0.01 to 100 parts by weight of a composition (2) consisting of 5 to 40% by weight of low density polyethylene of 0.940 g / cm ^3.
0.2 parts by weight, 0.01 to 0.1 parts by weight of a phosphorus-based antioxidant having a molecular weight of 500 or more, and hydrotalcite 0.1.
The resin composition (4) added with 01 to 0.1 parts by weight, the load at the time of 5% elongation of the (A) / (B) two-layer film in the machine direction is 400 gf / cm or more, and (C). A metallized multilayer film in which the layer is a metallized layer. 2. 0.01 to 0.2 part by weight of a phenolic antioxidant having a molecular weight of 500 or more and 100 parts by weight of composition (1) and 100 parts by weight of composition (2) and tris (2), respectively. , 4-di-t-butylphenyl) phosphite in an amount of 0.01 to 0.05 parts by weight and hydrotalcite in an amount of 0.01 to 0.1 parts by weight, and further added to the composition (1) 10
Anti-blocking agent 0.05 to 0.5 to 0 parts by weight
The metal vapor-deposited multilayer film according to claim 1, wherein parts by weight are added.