WO2010117066A1

WO2010117066A1 - Laminated film

Info

Publication number: WO2010117066A1
Application number: PCT/JP2010/056472
Authority: WO
Inventors: 真吾幸田; 省治西尾
Original assignee: 東ソー株式会社
Priority date: 2009-04-09
Filing date: 2010-04-09
Publication date: 2010-10-14

Abstract

Disclosed is a laminated film having excellent slip properties, which has excellent adhesion right after lamination molding and is capable of reducing the aging time for increasing the curing rate of a polyurethane adhesive. Specifically disclosed is a laminated film which is configured of four layers, namely a layer (A), a layer (B), a layer (C) and a layer (D). The layer (A) is configured from a resin composition A that is composed of an olefin polymer, and a fatty acid amide and/or an antistatic agent; the layer (B) is configured from a resin composition B that is composed of an olefin polymer, and an amine compound and/or a fatty acid metal salt that contains at least one metal selected from the group consisting of zinc, lithium, cobalt, iron and tin; the layer (C) is configured from a polyurethane adhesive and/or an isocyanate adhesive; and the layer (D) is configured of at least one or more base layers.

Description

Laminate film

The present invention relates to a laminate film. More specifically, it has excellent adhesiveness immediately after lamination molding without impairing the pot life of polyurethane adhesives and isocyanate adhesives, and can shorten the high-temperature aging treatment time performed after lamination molding. The present invention relates to an excellent laminate film.

Laminate film is widely adopted as a method that enables multifunctional packaging materials such as food packaging, medical products and medicine packaging, shampoo and cosmetic packaging. Such laminate films generally use an extrusion laminating method, a solvent-type dry laminating method, a solventless dry laminating method, etc., and a polyurethane adhesive or an isocyanate adhesive is applied to a substrate such as polyester, polyamide, or aluminum foil. It is manufactured by pasting together a polyolefin film. Polyurethane-based adhesives and isocyanate-based adhesives are applied to the surface of a substrate and cured after being bonded to a polyolefin film. However, these adhesives exhibit a high adhesive strength, but these adhesives have a slow curing reaction and are called aging. Heat treatment at about 40 ° C. is required for several days. Moreover, since the adhesive strength immediately after lamination is low due to the slow curing rate, adhesion failure such as tunneling may occur.

In addition, this aging treatment has a drawback that the higher aliphatic amide-based slip agent blended in the film is absorbed by the adhesive and deteriorates the openability (see, for example, Patent Documents 1 to 3). Therefore, a method for maintaining the slip property has been proposed.

For example, a method in which a general-purpose slip agent such as erucic acid amide and a slip agent that is difficult to be adsorbed to a laminating adhesive such as a high melting point fatty acid amide are used in combination (for example, Patent Documents 1, 4, and 5). A method (for example, Patent Documents 2 and 3) in which an amide and an inorganic filler having a large particle size are used in combination has been proposed. However, when such a high melting point fatty acid amide is used, the film surface is bleed and the surface appearance of the film is impaired, the guide roll of the laminating apparatus is contaminated, and the adhesion with the base material is deteriorated. There were problems such as.

Further, this aging treatment has a drawback that the antistatic agent blended in the film is absorbed by the adhesive and deteriorates the sustainability of the antistatic performance (see, for example, Patent Documents 6 to 9). Therefore, a method for maintaining the antistatic performance has been proposed.

For example, a method of using a general-purpose nonionic surfactant such as glycerin fatty acid ester and a surfactant such as organic sulfonate and polyglycerin fatty acid ester that are difficult to move in the film (for example, Patent Documents 6 and 7, And 8.), a method of preventing the movement of the antistatic agent by multilayering the film and providing a high-density, highly crystalline polymer layer in a part of the layers (for example, Patent Document 9) has been proposed. However, such surfactants that are difficult to move through the film have poor anti-bleeding performance due to poor bleedability to the film surface. On the other hand, multilayering with a high-density, highly crystalline polymer layer increases costs. There was a problem such as inviting.

Furthermore, many antistatic agents interfere with the curing reaction of polyurethane adhesives and isocyanate adhesives, and the antistatic agent may migrate to the adhesive layer before the adhesive is cured, resulting in poor adhesion. Therefore, although a method for selecting an antistatic agent having a low moving speed in a polymer such as polyglycerin fatty acid ester has been proposed (for example, Patent Document 10), there are problems such as insufficient antistatic performance. there were.

On the other hand, in order to shorten the aging treatment time, a method of adding a polyurethane curing catalyst to at least one of the films to be bonded has been proposed (for example, see Patent Document 11). However, the catalyst described in this document has a high possibility of adversely affecting the human body, such as an amine compound, an organic tin compound, and epsilon caprolactam, and cannot be used for food packaging, which is the main use of laminate films.

Japanese Unexamined Patent Publication No. 3-172328 Japanese Unexamined Patent Publication No. 6-312491 Japanese Unexamined Patent Publication No. 10-235815 Japanese Laid-Open Patent Publication No. 6-928 Japanese Unexamined Patent Publication No. 6-1894 Japanese Unexamined Patent Publication No. 2007-313737 Japanese Unexamined Patent Publication No. 2007-320219 Japanese Unexamined Patent Publication No. 2004-160964 Japanese Unexamined Patent Publication No. 2002-264283 Japanese Unexamined Patent Publication No. 2001-260284 US Pat. No. 6,074,755

The present invention has been made in view of the situation as described above, and has excellent adhesiveness immediately after laminate molding, can shorten the aging treatment time for increasing the curing rate of the polyurethane adhesive, and is excellent in slip properties. The object is to provide a film.

Another object of the present invention is to provide a laminate film that is excellent in adhesiveness immediately after laminate molding, can shorten the aging treatment time for increasing the curing rate of the polyurethane adhesive, and is excellent in antistatic properties. .

As a result of intensive studies to solve the above-mentioned problems, the present inventors have used a resin composition composed of a specific fatty acid metal salt and / or an amine compound for the olefin polymer as a laminate film, thereby bonding immediately after lamination. As a result, the present inventors have found that it has excellent slip properties and / or antistatic properties and has completed the present invention.

That is, the present invention comprises at least four layers of (A) layer / (B) layer / (C) layer / (D) layer, wherein (A) layer comprises 98 to 99.999% by weight of olefin polymer and fatty acid. The resin composition Aa composed of 0.001 to 2% by weight of amide is selected from the group consisting of 98 to 99.999% by weight of olefin polymer, zinc, lithium, cobalt, iron and tin. A resin composition B composed of 0.001 to 2% by weight of a fatty acid metal salt containing at least one metal and / or an amine compound, (C) the layer is a polyurethane-based adhesive and / or an isocyanate-based adhesive, (D ) The laminate film is characterized in that the layer comprises at least one base material.

Further, the present invention is composed of at least four layers of (A) layer / (B) layer / (C) layer / (D) layer, and the (A) layer comprises 98 to 99.999% by weight of olefin polymer and electrification. Resin composition Ab composed of 0.001 to 2% by weight of inhibitor, (B) layer selected from the group consisting of 98 to 99.999% by weight of olefin polymer, zinc, lithium, cobalt, iron and tin A resin composition B composed of 0.001 to 2% by weight of a fatty acid metal salt containing at least one metal and / or an amine compound, (C) the layer is a polyurethane-based adhesive and / or an isocyanate-based adhesive, D) The present invention relates to a laminate film characterized in that the layer comprises at least one base material.

Furthermore, the present invention relates to a laminate film, wherein the layer (A) is a resin composition Ac composed of 98 to 99.999% by weight of an olefin polymer, 0.001 to 2% by weight of a fatty acid amide and an antistatic agent. Is.

That is, the gist of the present invention resides in the following (1) to (13).

(1) It is composed of at least four layers of (A) layer / (B) layer / (C) layer / (D) layer, and (A) layer comprises 98 to 99.999% by weight of olefin polymer and 0. Resin composition Aa composed of 001 to 2% by weight, and (B) layer is at least one selected from the group consisting of 98 to 99.999% by weight of olefin polymer, zinc, lithium, cobalt, iron, and tin A resin composition B composed of 0.001 to 2% by weight of a fatty acid metal salt and / or an amine compound containing the above metal, (C) the layer is a polyurethane-based adhesive and / or isocyanate-based adhesive, and (D) the layer is A laminate film comprising at least one base material.

(2) It is composed of at least four layers of (A) layer / (B) layer / (C) layer / (D) layer, and (A) layer comprises 98 to 99.999% by weight of olefin polymer and antistatic agent 0. Resin composition Ab composed of 0.001 to 2% by weight, and (B) layer is at least one selected from the group consisting of 98 to 99.999% by weight of olefin polymer, zinc, lithium, cobalt, iron and tin Resin composition B composed of 0.001 to 2% by weight of fatty acid metal salt and / or amine compound containing seed metals, (C) layer is polyurethane adhesive and / or isocyanate adhesive, (D) layer A laminate film characterized by comprising a base material having at least one layer.

(3) It is composed of at least four layers of (A) layer / (B) layer / (C) layer / (D) layer, and the (A) layer comprises 96 to 99.998% by weight of olefin polymer, 0. Resin composition Ac composed of 001 to 2% by weight and antistatic agent 0.001 to 2% by weight, (B) layer is 98 to 99.999% by weight of olefin polymer, zinc, lithium, cobalt, iron, And a fatty acid metal salt containing at least one metal selected from the group consisting of tin and / or a resin composition B composed of 0.001 to 2% by weight of an amine compound, (C) the layer is a polyurethane adhesive and / or Alternatively, an isocyanate-based adhesive, (D) a laminate film comprising at least one base material.

(4) Preferably, the fatty acid metal salt constituting the resin composition B of the (B) layer is a fatty acid metal salt containing at least one metal selected from the group consisting of zinc, lithium, and cobalt. The laminate film according to any one of (1) to (3).

(5) Preferably, the amine compound constituting the resin composition B of the (B) layer is a polyoxyethylene alkylamine represented by the following general formula (I): (1) to (3 The laminate film according to any one of the above.

(Wherein R ¹ represents a linear or branched alkyl or alkenyl group having 8 to 30 carbon atoms, R ² and R ³ each independently represents —OCR ′ (R ′ represents a carbon atom having 8 to 30 carbon atoms) Represents a hydrogen group) or -H, and m and n are each independently an integer of 1 to 10.)
(6) The laminate film according to any one of (1) to (3), wherein the amine compound constituting the resin composition B of the layer (B) is a hindered amine light stabilizer.

(7) Preferably, the amine compound constituting the resin composition B of the (B) layer is an alkylamine represented by the following general formula (II), and any one of (1) to (3) The laminated film of crab.

(Wherein R ⁴ is a linear or branched fatty acid residue having 8 to 30 carbon atoms, R ⁵ and R ⁶ are each independently hydrogen, or a linear or branched chain having 1 to 8 carbon atoms. An alkyl group or an alkenyl group.)
(8) Preferably, any one of (1) and (4) to (7), wherein the surface resistivity of the surface on the (A) layer side of the laminate film is 10 ¹³ to 10 ¹⁷ (Ω) The laminate film described in 1.

(9) Preferably, the contact angle of water on the surface of the (A) layer side of the laminate film is 50 ° or more and 110 ° or less, according to any one of (1) and (4) to (8), Laminating film.

(10) Preferably, the antistatic agent constituting the resin composition Ab or the resin composition Ac of the layer (A) contains a glycerin fatty acid ester, and the laminate film according to (2) or (3) .

(11) The laminate according to (2) or (3), wherein the antistatic agent constituting the resin composition Ab or the resin composition Ac of the layer (A) preferably contains a polyglycerin fatty acid ester. the film.

(12) Preferably, the antistatic agent constituting the resin composition Ab or the resin composition Ac of the (A) layer contains an alkyl sulfonate, and the laminate according to (2) or (3) the film.

(13) Preferably, after laminate forming, the adhesive strength when left in an atmosphere at 23 ° C. for 5 minutes is 0.7 N / 25 mm or more, according to any one of (1) to (12) Laminate film.

The laminate film of the present invention is excellent as a packaging film for foods and the like with excellent productivity because it has excellent adhesiveness without being subjected to an aging treatment and can maintain good slip and antistatic properties for a long time. Useful for.

Hereinafter, the present invention will be described in detail.

The olefin polymer constituting the layers (A) and (B) of the present invention is a homopolymer of an α-olefin having 2 to 12 carbon atoms such as ethylene, propylene, 1-butene or a copolymer with a vinyl compound. Indicates. For example, low density polyethylene (LDPE), high density polyethylene, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, ethylene / 1-octene copolymer, ethylene-4-methyl-1-pentene Ethylene / α-olefin copolymers such as copolymers, ethylene / vinyl ester copolymers such as ethylene / vinyl acetate copolymers, ethylene / acrylic acid copolymers, ethylene / methacrylic acid copolymers, ethylene / acrylic Copolymer of ethylene and acrylic monomer such as acid ester copolymer, ethylene / methacrylic acid ester copolymer, and propylene such as polypropylene (PP), propylene / ethylene copolymer, propylene / 1-butene copolymer Polymers, poly 1-butene, poly 1-hexene, poly 4-methyl-1-pentene, etc. Such as olefin polymers. These olefin polymers may be used singly or in combination of two or more. Among these olefin polymers, low-density polyethylene, high-density polyethylene, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, ethylene A 1-octene copolymer is preferable, and an ethylene / 1-hexene copolymer, an ethylene / 1-octene copolymer, and a propylene-based polymer are particularly preferable from the viewpoint of film strength.

The fatty acid amide constituting the layer (A) of the present invention is added to improve the slip property of the laminate film, and is obtained by the reaction of the fatty acid with ammonia or an amine compound. Such fatty acid amides include caproic acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, myristoleic acid amide, palmitoleic acid amide, oleic acid amide, erucic acid amide and other fatty acid monoamides, ethylene Examples thereof include fatty acid bisamides such as bisstearic acid amide, ethylene bisoleic acid amide, ethylene bisbehenic acid amide, and ethylene biserucic acid amide. Such fatty acid amides may be used singly or in combination of two or more. Such fatty acid amides are commercially available from NOF Corporation under the trade name Alfro and Nippon Seika Co., Ltd. under the trade name Neutron.

Also, examples of the antistatic agent constituting the layer (A) of the present invention include nonionic surfactants, zwitterionic surfactants, and anionic surfactants that are used as antistatic agents for polyolefins.

Examples of the nonionic surfactant include glycerin fatty acid esters such as caproic acid glycerin ester, myristic acid glycerin ester, palmitic acid glycerin ester, stearic acid glycerin ester, oleic acid glycerin ester, and lauric acid glycerin ester; Polyglycerin fatty acid esters such as diglycerin ester, oleic acid diglycerin ester, stearic acid tetraglycerin ester; sorbitols; N, N-dihydroxyethylene stearylamine, polyoxyethylene stearylamine, polyoxyethylene laurylamine, polyoxypropylene Alkylamines such as stearylamine; polyoxyethylene stearyl amide, polyoxypropylene stearyl amide, etc. Alkyl amide such; capryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, oleyl alcohol, alcohols such as lauryl alcohol, and the like.
Examples of the zwitterionic surfactants include betaines such as alkylbetaines and alkylimidazolium betaines.
Further, as anionic surfactants, alkyl sulfonates such as sodium lauryl sulfonate, potassium lauryl sulfonate, sodium oleyl sulfonate, potassium oleyl sulfonate, sodium stearyl sulfonate, potassium stearyl sulfonate; potassium lauryl benzene sulfonate, Examples thereof include alkyl benzene sulfonates such as sodium oleyl benzene sulfonate, potassium oleyl benzene sulfonate, sodium stearyl benzene sulfonate, potassium stearyl benzene sulfonate, and alkyl phosphates.

Such surfactants can be used alone as an antistatic agent, or a plurality of such surfactants can be used in combination as an antistatic agent.

Among such antistatic agents, glycerin fatty acid esters, polyglycerin fatty acid esters, and alkyl sulfonates are preferable because they are excellent in antistatic properties and do not deteriorate adhesiveness, and are a combination of glycerin fatty acid ester and polyglycerin fatty acid ester. The combined use of glycerin fatty acid ester and alkylamide is particularly preferred.

A commercially available antistatic agent can be used. For example, RIKEN Vitamin “Riquemar” as glycerin fatty acid esters and polyglycerin fatty acid esters, “Monogli”, “Uniguri” from Nippon Oil & Fats, “Electro Stripper” from Kao, etc. “Atomer” from ICI as alkyl sulfonates, Examples include Lion's “Reostat” and Miyoshi oil and fat “Dasper”.

In the resin composition Aa constituting the layer (A) of the present invention, the olefin polymer is 98 to 99.999% by weight, the fatty acid amide is 0.001 to 2% by weight, preferably the olefin polymer 99 to 99.99. 995 wt%, fatty acid amide 0.005-1 wt%, more preferably olefin polymer 99.5-99.995 wt%, fatty acid amide 0.005-0.5 wt%, most preferably olefin polymer 99.7 to 99.99% by weight, and fatty acid amide 0.01 to 0.3% by weight. When the fatty acid amide is less than 0.001% by weight, the film surface is inferior in slipping property, and when the fatty acid amide exceeds 2% by weight, exudation from the laminate film becomes excessive, and the content is obtained when used as a packaging material. This is not preferable because the quality of the product may be impaired.

In the resin composition Ab constituting the layer (A) of the present invention, the olefin polymer is 98 to 99.999% by weight, the antistatic agent is 0.001 to 2% by weight, and preferably the olefin polymer 99 to 99. 0.95 wt%, antistatic agent 0.005 to 1 wt%, more preferably 99.5 to 99.995 wt% olefin polymer, and 0.005 to 0.5 wt% antistatic agent. When the antistatic agent is less than 0.001% by weight, the antistatic property of the film surface is inferior, which is not preferable. When the antistatic agent exceeds 2% by weight, exudation from the laminate film becomes excessive, and a packaging material is obtained. In some cases, the quality of the contents may be impaired.

In the resin composition constituting the layer (A) of the present invention, a fatty acid amide and an antistatic agent may be used in combination. In this case, the resin composition Ac contains the olefin polymer 96 to 99.998% by weight, the fatty acid amide 0.001 to 2% by weight, and the antistatic agent 0.001 to 2% by weight. And olefin polymer is preferably 98 to 99.99% by weight, fatty acid amide 0.005 to 1% by weight, and antistatic agent 0.005 to 1% by weight. preferable.

Further, additives used in ordinary olefin polymers such as an antioxidant, a neutralizing agent, an antiblocking agent, and a surfactant are added to the resin composition A constituting the present invention as necessary. It doesn't matter.

The resin composition A constituting the layer (A) of the present invention can be produced by a commonly used resin mixing apparatus. Examples thereof include a single-screw extruder, a twin-screw extruder, a Banbury mixer, a pressure kneader, a melt kneader such as a rotating roll, a Henschel mixer, a V blender, a ribbon blender, and a tumbler. When a melt kneader is used, the melting temperature is preferably about the melting point of the olefin polymer to about 350 ° C.

The thickness of the layer (A) constituting the present invention is not particularly limited as long as the object of the present invention is achieved, and is 1 μm to 5 mm in thickness because of excellent flexibility and small problems such as breakage. In view of economy, the range of 1 μm to 100 μm is most preferable.

The layer (A) of the present invention can be produced by a known film forming apparatus such as an inflation molding machine or a T-die casting machine. It is also possible to produce a molten film with an extrusion laminating machine.

The layer (A) of the present invention may be formed into a plurality of layers by a known co-extrusion film forming apparatus such as a co-extrusion inflation molding machine or a T-die cast molding machine. In this case, all the layers constituting the layer (A) may be constituted by the resin composition Aa, the resin composition Ab, or the resin composition Ac, but constitute the surface opposite to the surface in contact with the layer (B). Only the surface layer to be formed may be constituted by the resin composition Aa, the resin composition Ab, or the resin composition Ac.

The fatty acid metal salt constituting the layer (B) of the present invention contains at least one metal selected from the group consisting of zinc, lithium, cobalt, iron, and tin, and is bonded when the metal is zinc. The effect of improving the curing rate of the agent is preferable. One molecule or two or more fatty acids having different lengths and / or structures may be contained in one molecule.

Fatty acids constituting such fatty acid metal salts are saturated and / or unsaturated fatty acids having 4 to 30 carbon atoms, preferably 8 to 22 carbon atoms, more preferably 8 to 18 carbon atoms, and most preferably 8 to 14 carbon atoms. It is. Control of the fatty acid chain length is important because it determines the rate of transfer of the fatty acid metal salt to the adhesive. When the number of carbon atoms is 4 or more, the transfer amount to the polyurethane-based adhesive and / or the isocyanate-based adhesive increases, and the effect of improving the curing rate of the adhesive is high, which is preferable. When the number of carbon atoms is 30 or less, the amount of metal atoms is sufficient, and the effect of improving the curing rate of the adhesive is high, which is preferable. Such fatty acid metal salts include zinc octoate, zinc octenoate, zinc laurate, zinc stearate, zinc behenate, zinc 2-ethylhexanoate, lithium octoate, lithium laurate, lithium stearate, naphthenic acid. Examples include cobalt, cobalt stearate, dibutyltin oxide, dibutyltin malate, dibutyltin laurate, dioctyltin malate, dioctyltin laurate, iron laurate, iron stearate, and the like, zinc octoate, zinc octenoate, Zinc laurate, zinc stearate, zinc behenate, zinc 2-ethylhexanoate, lithium octoate, lithium laurate, lithium stearate, cobalt naphthenate, and cobalt stearate are particularly suitable. These fatty acid metal salts can be used alone or in combination. Among these fatty acid metal salts, fatty acid zinc salts are preferred because they have a high effect of shortening the aging time, and most preferred are carbons of fatty acids such as zinc octoate, zinc octenoate, zinc laurate, and zinc 2-ethylhexanoate. It is fatty acid zinc whose number is 8.

The amine compound constituting the layer (B) of the present invention is not particularly limited as long as it is a compound having an amino group in the molecule, but is a polyoxyethylene alkylamine represented by the following general formula (I) , Hindered amine light stabilizers, and alkylamines represented by the following general formula (II) are preferable because of excellent adhesiveness, and polyoxyethylene alkylamines represented by the following general formula (I) are most preferable. These amine compounds can be used alone or in combination of two or more.

(Wherein R ¹ represents a linear or branched alkyl or alkenyl group having 8 to 30 carbon atoms, R ² and R ³ each independently represents —OCR ′ (R ′ represents a carbon atom having 8 to 30 carbon atoms) Represents a hydrogen group) or -H, and m and n are each independently an integer of 1 to 10.)

(Wherein R ⁴ is a linear or branched fatty acid residue having 8 to 30 carbon atoms, R ⁵ and R ⁶ are each independently hydrogen, or a linear or branched chain having 1 to 8 carbon atoms. An alkyl group or an alkenyl group.)
The carbon number of R ¹ , R ² , or R ³ constituting such a polyoxyethylene alkylamine is important for determining the transfer rate of the polyoxyethylene alkylamine to the adhesive, and the carbon number is 8 -30, preferably 8-22. When R ¹ , R ² , or R ³ has 8 or more carbon atoms, the transfer amount to the polyurethane-based adhesive and / or isocyanate-based adhesive increases, and the effect of improving the curing rate of the adhesive is high, which is preferable. Further, when the number of carbon atoms is 30 or less, the amount of amino groups is increased, and the effect of improving the curing rate of the adhesive is high, which is preferable. Examples of such polyoxyethylene alkylamine include dodecyldioxyethylamine, tetradecyldioxyethylamine, octadecyldioxyethylamine, 16-oxyheptadecyldioxyethylamine, octadecyloxyethoxyethylamine, 17-octadecenyldioxyethylamine, Examples thereof include 1-methylheptadecyldioxyethylamine. Such polyoxyethylene alkylamines may be used singly or in combination of two or more.

Such polyoxyethylene alkylamines can be obtained from commercial products, such as Naimine L-201, Naimine L-202, Naimine L-207, Naimeen S-202, Naimeen S-204, Naimeen from NOF Corporation. They are sold under the names S-210, Naimine O-205, Naimine T2-202, and the like.

The hindered amine light stabilizer constituting the present invention is a compound having a piperidine ring in the molecule and a structure in which hydrogen on carbons at the 2nd and 6th positions of the piperidine ring is substituted with a methyl group. Such a hindered amine light stabilizer is not particularly limited, and examples thereof include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and dimethyl-1- (2-hydroxyethyl) succinate. -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate 2,2,6,6-tetramethyl-4-piperidinylbenzoate, bis (1,2,6,6-tetramethyl-4-piperidinyl) -2- (3,5-di-t-butyl- 4-hydroxybenzyl) -2-n-butylmalonate, bis (N-methyl-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 1,1 ′-(1,2-ethanediyl Bis (3,3,5,5-tetramethylpiperazinone), (mixed 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate , (Mixed 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, mixed {2,2,6,6-tetramethyl- 4-piperidyl / β, β, β ′, β′-tetramethyl-3-9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethyl} -1,2,3,4 -Butanetetracarboxylate, mixed {1,2,2,6,6-pentamethyl-4-piperidyl / β, β, β ′, β′-tetramethyl-3-9- [2,4,8,10 -Tetraoxaspiro (5,5) undecane Diethyl} -1,2,3,4-butanetetracarboxylate, N, N′-bis (3-aminopropyl) ethylenediamine-2--4-bis [N-butyl-N- (1,2,2,6) , 6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylene Condensation product of diamine and 1,2-dibromoethane, [N- (2,2,6,6-tetramethyl-4-piperidyl) -2-methyl-2- (2,2,6,6-tetramethyl) -4-piperidyl) imino] propionamide, poly {[6-[(1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4-diyl] [[(2 , 2,6,6-Tetramethyl-4-piperidyl Imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]}, poly {2,2,4,4-tetramethyl-7-oxa-3,20-diaza-20 ( 2,3-epoxypropyl) dispiro [5.1.1.1.2] heneicosan-21-one}, 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-dispiro [5.1 11.2] heneicosan-21-one, 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-dispiro [5.1.1.12] heneicosane-20-propanoic acid And dodecyl ester / tetradecyl ester. Such a hindered amine light stabilizer can be obtained from a commercial product, for example, sold under the trade names of Ciba Japan Co., Ltd., Tinuvin, Clariant Japan Co., Ltd., Hostabin, and Adeka Co., Ltd., Adeka Stub. The hindered amine light stabilizer may be used not only alone but also in combination of two or more different structures.

The carbon number of the R ⁴ group constituting the alkylamine represented by the following general formula (II) is important for determining the transfer rate of the alkylamine to the adhesive, and preferably has 8 to 30 carbon atoms. Yes, more preferably 8-22. When the number of carbon atoms in the R ⁴ group is within this range, the mobility to the polyurethane adhesive and / or the isocyanate adhesive is excellent, and the effect of improving the curing rate of the adhesive is high, which is preferable. Further, when the number of carbon atoms in the R ⁵ or R ⁶ group is within this range, the effect of improving the curing rate of the adhesive is high, which is preferable. Such alkylamines may be used singly or in combination of two or more.

Examples of such alkylamines include laurylamine, myristylamine, stearylamine, oleylamine, behenylamine, dimethyllaurylamine, dimethylmyristylamine, dimethylpalmitylamine, dimethylstearylamine, and the like from NOF Corporation. Nissan amine BB, Nissan amine AB, Nissan amine OB, tertiary Nissan amine BB, tertiary Nissan amine AB and the like.

Also, these amine compounds and fatty acid metal salts containing at least one metal selected from the group consisting of zinc, lithium, cobalt, iron, and tin can be used in combination.

The blend in the resin composition B constituting the layer (B) of the present invention is at least one selected from the group consisting of 98 to 99.999% by weight of an olefin polymer, zinc, lithium, cobalt, iron, and tin. A metal-containing fatty acid metal salt and / or an amine compound of 0.001 to 2% by weight, preferably 99 to 99.995% by weight of an olefin polymer, at least selected from the group consisting of zinc, lithium, cobalt, iron, and tin Fatty acid metal salt containing one kind of metal and / or amine compound 0.005 to 1% by weight, more preferably 99.5 to 99.995% by weight, zinc, lithium, cobalt, iron, and tin Fatty acid metal salt and / or amine compound containing at least one metal selected from the group consisting of 0.005 to 0.5% by weight, most preferably olefin Fatty acid metal salt and / or amine compound 0.01 to 0 containing at least one metal selected from the group consisting of 99.7 to 99.99% by weight of a polymer and zinc, lithium, cobalt, iron and tin .3% by weight. When the fatty acid metal salt and / or amine compound containing at least one metal selected from the group consisting of zinc, lithium, cobalt, iron, and tin is less than 0.001% by weight, the effect of improving the curing rate of the adhesive is low. Therefore, when the amount of the fatty acid metal salt and / or amine compound containing at least one metal selected from the group consisting of zinc, lithium, cobalt, iron, and tin exceeds 2% by weight, exudation from the laminate film occurs. It is not preferable because it becomes excessive and may deteriorate the quality of the contents when used as a packaging material.

In addition, the resin composition B constituting the layer (B) of the present invention may be added to an olefin resin usually used for an antioxidant, a lubricant, an inorganic filler, a surfactant, a slip agent, etc. as necessary. You may add the agent in the range which does not impair adhesiveness.

The resin composition B constituting the layer (B) of the present invention can be produced by a commonly used resin mixing apparatus. Examples thereof include a single-screw extruder, a twin-screw extruder, a Banbury mixer, a pressure kneader, a melt kneader such as a rotating roll, a Henschel mixer, a V blender, a ribbon blender, and a tumbler. When a melt kneader is used, the melting temperature is preferably about the melting point of the olefin polymer to about 350 ° C.

The thickness of the layer (B) constituting the present invention is not particularly limited as long as the object of the present invention is achieved, and is 1 μm to 5 mm in thickness because of excellent flexibility and small problems such as breakage. In view of economy, the range of 1 μm to 100 μm is most preferable.

The layer (B) of the present invention can be produced by a known film forming apparatus such as an inflation molding machine or a T die cast molding machine. It is also possible to produce a molten film with an extrusion laminating machine.

In order to increase the curing rate of the adhesive used for the (C) layer and to obtain good adhesive performance, the surface of the (B) layer of the present invention that is in contact with the (C) layer is It is preferable that the contact surface to be in contact is oxidized.

(B) Examples of oxidation treatment methods for oxidizing the layer surface include chromic acid treatment, sulfuric acid treatment, air oxidation, ozone treatment, corona discharge treatment, flame treatment, plasma treatment, etc. For effective formation, corona discharge treatment, flame treatment, plasma treatment and / or ozone treatment are particularly preferred.

Corona discharge treatment is widely used as a continuous treatment technique for plastic film and sheet surfaces, and is performed by passing the film through a corona atmosphere generated by a corona discharge treatment machine. The corona discharge density is preferably 1 to 100 W · min / m ² , since the curing rate of the adhesive can be increased and good adhesive performance can be obtained.

The flame treatment is performed by bringing the film surface into contact with a flame generated when natural gas or propane is burned.

Plasma treatment is an excited inert gas that is electrically neutral after removing charged particles by electronically exciting a single or mixed gas such as argon, helium, neon, hydrogen, oxygen, and air with a plasma jet. Is sprayed onto the film surface.

Moreover, when it uses for extrusion lamination molding, in order to acquire favorable adhesiveness, the surface which contact | connects the base material of the (B) layer extruded from die | dye can be oxidized by air oxidation or ozone treatment. When the oxidation reaction with air proceeds, the temperature of the resin composition for extrusion lamination of the present invention extruded from the die is preferably 290 ° C. or higher. When the oxidation reaction with ozone gas proceeds, the resin composition was extruded from the die. The temperature of the resin composition for extrusion lamination of the present invention is preferably 200 ° C. or higher. Moreover, it is preferable that it is 0.5 mg or more per 1 m < ² > of films which consist of the resin composition for extrusion laminations of this invention extruded from die | dye as a processing amount of ozone gas.

The polyurethane adhesive and the isocyanate adhesive constituting the layer (C) of the present invention are not particularly limited, and known ones can be used.

The polyurethane-based adhesive is composed of at least one polyol component having at least two hydroxyl groups in the molecule and at least one polyisocyanate component and / or diisocyanate having at least two isocyanate groups in the molecule. It is preferable that the adhesive is constituted. The polyol component can be appropriately selected from polyester polyols, polyether polyols, acrylic polyols, polyolefin polyols, and the like, and polyester polyols are particularly preferable because they have a high function of suppressing deterioration of adhesiveness with the (C) layer over time. Diisocyanates include 4,4′-, 2,4′- and 2,2′-diisocyanate diphenylmethane, 1,5-diisocyanate naphthalene, 4,4′-diisocyanate dicyclohexylmethane, 1,4-diisocyanate benzene, and / or Aromatic diisocyanates such as 2,4- or 2,6-diisocyanate toluene, 1,6-diisocyanate hexane, 1,10-diisocyanate decane, 1,3-diisocyanate cyclopentane, 1,4-diisocyanate cyclohexane, 1-isocyanate- Illustrative are aliphatic and cycloaliphatic diisocyanates such as 3,3,5-trimethyl-3 or -5-isocyanatomethanecyclohexane. The polyisocyanate component can be produced from these diisocyanate monomers.

As polyurethane-based adhesives, manufactured by Dainichi Seika Kogyo Co., Ltd., trade names Seika Bond E-263, Seika Bond C-26, manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., trade names Takelac A3210, Takenate A3072, etc. Commercial products such as Coronate L manufactured by Nippon Polyurethane Industry Co., Ltd. can be used.

These polyurethane-based adhesives or isocyanate-based adhesives can be blended with reaction catalysts and other additives within a range that does not adversely affect adhesiveness and pot life.

Examples of the isocyanate-based adhesive include those having the above polyisocyanate and / or diisocyanate as the main component and an amine compound or the like as a curing agent.

The thickness of these adhesives is not particularly limited, but is preferably 0.01 to 10 μm because the effect of improving the curing rate of the adhesive is high, and more preferably 0.1 to 6 μm.

The adhesive is applied to the substrate and / or the polyolefin film with a coater attached to a known extrusion laminator, solvent-type dry laminator, or solventless dry laminator.

The solvent used for diluting the adhesive is not particularly limited, but esters such as ethyl acetate, butyl acetate and cellosolve acetate, ketones such as acetone, methyl ethyl ketone, isobutyl ketone and cyclohexanone, tetrahydrofuran, dioxane and the like Exemplified ethers, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and ethylene chloride, alcohols such as dimethyl sulfoxide, dimethyl sulfoamide, methanol, ethanol and isopropanol, water, etc. be able to.

Examples of the base material constituting the layer (D) of the present invention include a synthetic polymer film or sheet, woven fabric, non-woven fabric, paper, and metal foil. Examples of the synthetic polymer film or sheet include a film or sheet made of a synthetic polymer such as polyester such as polyethylene terephthalate, polyamide, polyvinyl alcohol, saponified ethylene / vinyl acetate copolymer, polycarbonate, polyethylene, or polypropylene. Furthermore, these polymer films or sheets may have a surface deposited with aluminum, alumina, silica or the like, or may have a surface printed with urethane-based ink or the like. Examples of the woven or non-woven fabric include those made of synthetic resin such as polyester, polyethylene, and polypropylene, or those made of natural materials such as sufu. Examples of the paper include craft paper, kulpack paper, high-quality paper, glassine paper, and paperboard. In addition to the use of these substrates alone, those obtained by laminating them can also be used.

The laminate film of the present invention is composed of four layers of (A) layer / (B) layer / (C) layer / (D) layer. May be included.

The laminate film of the present invention is bonded to the (B) layer and the substrate via the (C) layer using a known extrusion laminate molding machine, solvent-type dry laminate molding machine, solventless dry laminate molding machine, or the like. Can be manufactured. Although the manufacturing method of a laminate film is illustrated below, it is not limited to these methods.
-After coating the (C) layer on the (D) layer, the (B) layer and the (A) layer are sequentially laminated by a tandem extrusion laminator.
-After the (C) layer is applied to the (D) layer, the (B) layer is melt-laminated between the previously produced (A) layer film and the (C) layer by a sandwich extrusion laminator.
-After coating (C) layer on (D) layer, (B) layer and (A) layer are laminated | stacked simultaneously by a coextrusion laminator.
-After the (C) layer is applied to the (D) layer, a film in which the (B) layer and the (A) layer previously produced by a coextrusion film forming machine are laminated is dry-laminated.

The laminate film of the present invention may be subjected to a heat treatment (aging treatment) at 30 ° C. or higher, which is performed after known extrusion laminate molding, solvent-type dry laminate molding, or solvent-free dry laminate molding. Therefore, it is possible to eliminate the heat treatment.

At that time, it is preferable that the adhesive strength when left for 5 minutes in an atmosphere at 23 ° C. after the laminate molding is 0.7 N / 25 mm or more because it is possible to avoid adhesion trouble such as tunneling, and more preferably 1. 0 N / 25 mm or more. A laminate film satisfying this range can be suitably obtained by controlling the compounding ratio of the amine compound having alkyl and the fatty acid metal salt, the thickness of the polyolefin film, and the coating amount of the polyurethane adhesive.

Also, it is preferable that the adhesive strength when left for 700 minutes in an atmosphere at 23 ° C. after lamination is 10 N / 25 mm or more because aging treatment can be made unnecessary.

Furthermore, if the time for which the sealing strength of the laminate film when left in an atmosphere at 23 ° C. after lamination is 80% of the sealing strength for 72 hours in an atmosphere at 40 ° C. is within 12 hours, This is preferable because it is possible to improve the protection of the contents when avoiding the packaging and the packaging bag.

In the laminate film of the present invention, when the resin composition Aa or the resin composition Ac is used for the (A) layer, the surface specific resistance value on the (A) layer side surface is 10 ¹³ to 10 ¹⁷ (Ω). If it is in the range, it is preferable because a decrease in adhesive strength over time can be suppressed, and 10 ¹⁴ to 10 ¹⁷ (Ω) is more preferable. A laminate film satisfying this range can be appropriately obtained by controlling the blending ratio of the fatty acid metal salt and / or amine compound, the thickness of the (B) layer, the amount of polyurethane adhesive and / or isocyanate adhesive applied. Can do.

In the laminate film of the present invention, when the resin composition Ab or the resin composition Ac is used for the (A) layer, the surface specific resistance value on the (A) layer side surface is 10 ⁸ to 10 ¹⁴ (Ω). If it is in the range, it is preferable because it can suppress a decrease in adhesive strength over time, and more preferably 10 ⁸ to 10 ¹³ (Ω). Laminate films satisfying this range are blended proportions of antistatic agent, blended proportions of the fatty acid metal salt and / or amine compound, (A) layer and / or (B) layer thickness, polyurethane adhesive and / or isocyanate. It can be suitably obtained by controlling the coating amount of the system adhesive. The surface resistivity was measured using TR8601 and TR-42 manufactured by Advantest Co., Ltd., and the resistivity on the surface of the laminate after 1 minute at an applied voltage of 500 kV in an environment of 23 ° C. and 50% RH. It can be obtained by reading.

Such laminate film can be used as a wide range of packaging materials such as snack foods, dried foods such as instant noodles, soups, miso, pickles, beverages and other aquatic foods and drinks, medicines such as infusion bags, shampoos and cosmetics. it can.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

(1) Melt mass flow rate (MFR)
In the case of an ethylene polymer, the measurement was conducted according to JIS K6922-1 (1997), and in the case of a propylene polymer, the measurement was conducted in accordance with JIS K7210.

(2) Density The density was measured in accordance with JIS K6922-1 (1997).

(3) Adhesive properties Polyester (PET) film and polyolefin film obtained by cutting the laminate film obtained in Examples into a shape having a width of 25 mm and a length of 100 mm and bonding them with a polyurethane adhesive and / or an isocyanate adhesive The adhesive strength between them was measured with Autograph DCS-100 (manufactured by Shimadzu Corporation). The measurement was performed after 5 minutes and 700 minutes after the lamination. The peeling speed is 300 mm / min. In addition, the laminate film storage temperature from laminate molding to peel strength measurement is 23 ° C.

(4) Seal strength development time The polyolefin film surfaces of the laminate film obtained in the examples were heat-sealed under the conditions of a temperature of 150 ° C., a pressure of 0.1 MPa, and a time of 1 second. The heat-sealed film was cut into a shape having a width of 15 mm and a length of 100 mm, and the peel strength of the heat-sealed portion was measured with Autograph DCS-100 (manufactured by Shimadzu Corporation). The measurement was performed at intervals of 1 hour between 1 and 16 hours after lamination, and thereafter at intervals of 12 hours and 72 hours after 24 hours. The sample used was left in a 23 ° C. atmosphere after lamination. The peeling speed is 300 mm / min. The time when 80% strength of the seal strength of the sample left in an atmosphere of 40 ° C. for 72 hours was developed was defined as the seal strength development time.

(5) Surface resistivity value The laminate film obtained by the example after 1 minute at an applied voltage of 500 kV under an environment of 23 ° C. and 50% RH using TR8601 and TR-42 manufactured by Advantest Co., Ltd. (A ) The specific resistance value of the layer side surface was measured.

(6) Contact angle of water Using the automatic contact angle / interfacial tension meter PD-Z manufactured by Kyowa Interface Science Co., Ltd., under the environment of 23 ° C. and 50% RH, (A ) The contact angle immediately after dropping pure water on the layer side surface was determined.

(7) Slip property (A) layer surface of the laminate film obtained by the Example was measured based on JIS K7125 (1999), and μK (dynamic friction coefficient) was measured. The laminate film used for the measurement was a laminate film which was left in an atmosphere at 23 ° C. after being molded. However, some of the samples with insufficient adhesion were subjected to an aging treatment for 72 hours in an atmosphere at 40 ° C.

Example 1
Low-density polyethylene having an MFR of 8 g / 10 min and a density of 918 kg / m ³ as an olefin polymer (trade name Petrocene 213 manufactured by Tosoh Corporation, hereinafter sometimes referred to as PE-B) 99.95% by weight Polyoxyethylene dodecylamine (trade name: Naimine L-202 manufactured by NOF Corporation, hereinafter sometimes referred to as CAT-1) as a polyoxyethylene alkylamine is blended so as to be 0.05% by weight. The mixture was melt-kneaded with a shaft extruder (Laboplast Mill, manufactured by Toyo Seiki Seisakusho Co., Ltd.) to obtain pellets of the resin composition B used for the (B) layer.

In the same manner, as an olefin polymer, a mixture of an ethylene / 1-hexene copolymer having an MFR of 10 g / 10 min and a density of 913 kg / m ³ and a low density polyethylene (trade name Nipolon- manufactured by Tosoh Corporation) Z TZ420 (hereinafter sometimes referred to as PE-A) is 99.98% by weight, and erucic acid amide (trade name Alflow P-10 manufactured by NOF Corporation) as the fatty acid amide is sometimes referred to as FA-1. ) Was blended to 0.02% by weight, and melt-kneaded with a twin screw extruder (Laboplast Mill, manufactured by Toyo Seiki Seisakusho Co., Ltd.) to obtain pellets of the resin composition Aa used for the layer (A).

A 90 mmφ / 65 mmφ coextrusion laminator (manufactured by Placo) was used for the production of the laminate film. The obtained resin composition B pellets are supplied to an extruder having a 90 mmφ screw, and the resin composition Aa pellets are supplied to an extruder having a 65 mmφ screw, and are coextruded from a T die at a temperature of 320 ° C. (D) layer (C) on the corona-treated surface of a biaxially stretched polyester film (trade name ester film E-5100, manufactured by Toyobo Co., Ltd., thickness 25 μm, hereinafter referred to as PET) A laminate film is obtained by coextruding and laminating a resin composition B to a thickness of 20 μm and a resin composition A to a thickness of 40 μm on a base material obtained by applying a polyurethane adhesive blended in the following ratio as a layer and drying the solvent. Obtained.

Formulation of polyurethane adhesive: Takelac A3210 (15 parts) + Takenate A3072 (5 parts) + ethyl acetate (140 parts)
Both Takelac A3210 and Takenate A3072 are manufactured by Mitsui Chemicals Polyurethanes Co., Ltd. Adhesive thickness: 0.2 μm
The physical properties of the obtained laminate film are shown in Table 1.

Example 2
As resin composition B, instead of 99.95% by weight of PE-B and 0.05% by weight of CAT-1, 99.95% by weight of PE-B, zinc distearate (manufactured by NOF Corporation) A laminate film was obtained in the same manner as in Example 1, except that the nominal zinc stearate (hereinafter sometimes referred to as CAT-2) was 0.05% by weight. The evaluation results are shown in Table 1.

Example 3
As resin composition B, PE-B was 99.95% by weight, CAT-1 was 0.05% by weight, PE-B was 99.90% by weight, and CAT-2 was 0.10% by weight. Except for the above, a laminate film was obtained in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 4
As resin composition B, PE-B was 99.95 wt%, CAT-1 was 0.05 wt%, PE-B was 99.80 wt%, and CAT-2 was 0.20 wt%. Except for the above, a laminate film was obtained in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 5
As resin composition B, instead of 99.95% by weight of PE-B and 0.05% by weight of CAT-1, 99.90% by weight of PE-B, zinc dilaurate (manufactured by NOF Corporation) A laminate film was obtained in the same manner as in Example 1 except that the nominal gin laurate (hereinafter sometimes referred to as CAT-3) was 0.1% by weight. The evaluation results are shown in Table 1.

Example 6
As resin composition B, instead of 99.95% by weight of PE-B and 0.05% by weight of CAT-1, 99.90% by weight of PE-B and poly {[6- [ (1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4-diyl] [[(2,2,6,6-tetramethyl-4-piperidyl) imino] Hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]} (Ciba Japan Co., Ltd. trade name Kimasorb 944FDL, hereinafter sometimes referred to as CAT-4) 0.10 weight A laminated film was obtained in the same manner as in Example 1 except that the content was%. The evaluation results are shown in Table 1.

Example 7
As resin composition B, instead of 99.95% by weight of PE-B and 0.05% by weight of CAT-1, 99.90% by weight of PE-B, amine dimethylstearate (manufactured by NOF Corporation) A laminate film was obtained in the same manner as in Example 1 except that the trade name of tertiary amine AB (hereinafter sometimes referred to as CAT-5) was changed to 0.10% by weight. The evaluation results are shown in Table 1.

Example 8
As resin composition Aa, PE-A was changed to 99.98 wt%, FA-1 was changed to 0.02 wt%, PE-A was changed to 99.92 wt%, and FA-1 was changed to 0.08 wt%. Except for the above, a laminate film was obtained in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 9
As resin composition Aa, PE-A 99.98 wt%, FA-1 0.02 wt% instead of PE-A 99.98 wt%, ethylenebisoleic acid amide (NOF Corporation) A laminate film was obtained in the same manner as in Example 1 except that the product name Alflow AD281-F (hereinafter sometimes referred to as FA-2) was 0.02 wt%. The evaluation results are shown in Table 1.

Example 10
As resin composition B, instead of 99.95% by weight of PE-B and 0.05% by weight of CAT-1, 99.90% by weight of PE-B and 2-ethyl-zinc hexanoate (Nippon Chemical Industry ( A laminate film was obtained in the same manner as in Example 1 except that the product name Nikka Octix Zinc (18%, hereinafter may be referred to as CAT-6) was 0.1% by weight. The evaluation results are shown in Table 1.

Comparative Example 1
Laminate film in the same manner as in Example 1 except that the resin composition B was changed to 99.95% by weight of PE-B and 0.05% by weight of CAT-1 but 100% by weight of PE-B. Got. The evaluation results are shown in Table 2. Both the initial adhesive strength (after 5 minutes) and the adhesive strength after 700 minutes were low and inferior. Moreover, since the adhesive strength was low in the slip property evaluation, a sample subjected to an aging treatment for 72 hours in an atmosphere at 40 ° C. was used, but the static friction coefficient was high and the slip property was poor.

Comparative Example 2
As resin composition B, PE-B was changed to 99.95 wt%, CAT-1 was changed to 0.05 wt%, PE-B was changed to 97.80 wt%, and CAT-1 was changed to 2.2 wt%. Except for the above, a laminate film was obtained in the same manner as in Example 1. The evaluation results are shown in Table 2. Both the initial adhesive strength (after 5 minutes) and the adhesive strength after 700 minutes were low and inferior. Moreover, since the adhesive strength did not increase after aging treatment for 72 hours in an atmosphere at 40 ° C., the slip property was not evaluated.

Comparative Example 3
As resin composition B, instead of 99.95% by weight of PE-B and 0.05% by weight of CAT-1, 99.90% by weight of PE-B, calcium distearate (manufactured by NOF Corporation) A laminate film was obtained in the same manner as in Example 1 except that the nominal calcium stearate G (hereinafter sometimes referred to as CAT-7) was 0.10% by weight. The evaluation results are shown in Table 2. Both the initial adhesive strength (after 5 minutes) and the adhesive strength after 700 minutes were low and inferior. Moreover, since the adhesive strength was low in the slip property evaluation, a sample subjected to an aging treatment for 72 hours in an atmosphere at 40 ° C. was used, but the static friction coefficient was high and the slip property was poor.

Comparative Example 4
A laminate film as in Example 1 except that the resin composition Aa was changed to 99.98% by weight of PE-A and 100% by weight of PE-A instead of 0.02% by weight of FA-1. Got. The evaluation results are shown in Table 2. The static friction coefficient was high and the slip property was inferior.

Comparative Example 5
As the resin composition Aa, PE-A was changed to 99.98 wt%, FA-1 was changed to 0.02 wt%, PE-A was changed to 97.8 wt%, and FA-1 was changed to 2.2 wt%. Except for the above, an attempt was made to produce a laminate film in the same manner as in Example 1, but the smoke generation during the laminate molding was so severe that a laminate film could not be obtained.

Example 11
As an olefin polymer, a propylene polymer having a MFR of 6.5 g / 10 min and a density of 900 kg / m ³ (manufactured by Nippon Polypro Co., Ltd., trade name: FW4BT, hereinafter may be referred to as PP) 99 90% by weight and CAT-2 in an amount of 0.10% by weight, and melt-kneaded with a twin screw extruder (Laboplast Mill, manufactured by Toyo Seiki Seisakusho Co., Ltd.) 1 pellet was obtained.

Similarly, 99.96% by weight of PP and 0.04% by weight of FA-1 are blended, and melt-kneaded with a twin screw extruder (Laboplast Mill, manufactured by Toyo Seiki Seisakusho Co., Ltd.). A pellet of composition Aa-1 was obtained.

For film molding, a three-type three-layer coextrusion cast film molding machine (manufactured by Plastics Engineering Laboratory) was used. The above resin composition Aa-1 pellets are placed in the extruder constituting one surface layer (A layer), and the resin composition B-1 pellets are placed in the extruder constituting the other two layers (B1 layer, B2 layer). After feeding and extruding from a T-die at a temperature of 220 ° C. to obtain a multilayer film composed of (A) layer / (B1) layer / (B2) layer, the condition of 30 W · min / m ² on the surface of (B2) layer The corona treatment was applied. The thickness of each layer was 20 μm.

For the lamination molding, a solvent-type dry laminator (manufactured by Inoue Metal Industry Co., Ltd.) was used. Polyurethane adhesive compounded at the ratio shown below is applied to the corona-treated surface of a biaxially stretched polyester film (trade name ester film E-5100, manufactured by Toyobo Co., Ltd., thickness 25 μm, hereinafter sometimes referred to as PET) Then, the substrate dried with the solvent and the corona-treated surface of the film were bonded together to obtain a laminate film.

Formulation of polyurethane adhesive: Seika Bond E-263 (25 parts) + Seika Bond C-26 (5 parts) + ethyl acetate (150 parts)
Seika Bond is manufactured by Dainichi Seika Kogyo Co., Ltd. Adhesive thickness: 3μm
The adhesive strength of the obtained laminate film is shown in Table 3.

Example 12
Instead of the resin composition B-1, an ethylene / 1-hexene copolymer having a MFR of 2 g / 10 min and a density of 920 kg / m ³ (trade name Nipolon Z-ZF230, manufactured by Tosoh Corp., hereinafter referred to as PE -C) may be changed to Resin Composition B-2 with 99.90% by weight and CAT-2 at 0.10% by weight, and PE-C may be used instead of Resin Composition Aa-1. A laminate film was obtained in the same manner as in Example 10, except that the resin composition Aa-2 was changed to 99.96 wt% and FA-1 0.04 wt%.

The adhesive strength of the obtained laminate film is shown in Table 3.

Example 13
Instead of resin composition Aa-1, PE-C was changed to resin composition Aa-3 with 99.96 wt%, FA-1 0.02 wt%, and FA-2 0.02 wt%. Except for the above, a laminate film was obtained in the same manner as in Example 11.

The adhesive strength of the obtained laminate film is shown in Table 3.

Example 14
Low-density polyethylene having an MFR of 8 g / 10 min and a density of 918 kg / m ³ as an olefin polymer (trade name Petrocene 213 manufactured by Tosoh Corporation, hereinafter sometimes referred to as PE-B) 99.95% by weight , Polyoxyethylene dodecylamine (CAT-1) as polyoxyethylene alkylamine was mixed at 0.05% by weight, and melt kneaded with a twin screw extruder (laboroplast mill manufactured by Toyo Seiki Seisakusho Co., Ltd.). (B) The pellet of the resin composition B used for a layer was obtained.

In the same manner, 99.80 wt. Of a mixture (PE-A) of an ethylene / 1-hexene copolymer having a MFR of 10 g / 10 min and a density of 913 kg / m ³ and a low density polyethylene was used as the olefin polymer. 0.1% by weight of stearic acid glycerin ester (trade name Riquemar S-100 manufactured by Riken Vitamin Co., Ltd., hereinafter sometimes referred to as AS-1) as an antistatic agent, stearic acid polyglycerin ester (RIKEN vitamin) A product name Riquemar S-71D (hereinafter referred to as “AS-2”) may be blended to 0.1% by weight, and a twin screw extruder (labor plast mill manufactured by Toyo Seiki Seisakusho Co., Ltd.) And kneaded to obtain pellets of the resin composition Ab used for the layer (A).

A 90 mmφ / 65 mmφ coextrusion laminator (manufactured by Placo) was used for the production of the laminate film. The obtained resin composition B pellets are supplied to an extruder having a 90 mmφ screw, and the resin composition Ab pellets are supplied to an extruder having a 65 mmφ screw, and are coextruded from a T die at a temperature of 320 ° C. (D) layer (C) on the corona-treated surface of a biaxially stretched polyester film (trade name ester film E-5100, manufactured by Toyobo Co., Ltd., thickness 25 μm, hereinafter referred to as PET) A laminate film is obtained by coextrusion laminating a resin composition B to a thickness of 20 μm and a resin composition Ab to a thickness of 40 μm on a base material obtained by applying a polyurethane adhesive blended in the ratio shown below as a layer and drying the solvent. Obtained.

Formulation of polyurethane adhesive: Takelac A3210 (15 parts) + Takenate A3072 (5 parts) + ethyl acetate (140 parts)
Both Takelac A3210 and Takenate A3072 are manufactured by Mitsui Chemicals Polyurethanes Co., Ltd. Adhesive thickness: 0.2 μm
Table 4 shows the physical properties of the obtained laminate film.

Example 15
As resin composition B, instead of 99.95% by weight of PE-B and 0.05% by weight of CAT-1, 99.95% by weight of PE-B and 0. 5% of zinc distearate (CAT-2) were added. A laminate film was obtained in the same manner as in Example 14 except that the content was changed to 05% by weight. The evaluation results are shown in Table 4.

Example 16
As resin composition B, PE-B was 99.95% by weight, CAT-1 was 0.05% by weight, PE-B was 99.90% by weight, and CAT-2 was 0.10% by weight. A laminated film was obtained in the same manner as in Example 14 except that. The evaluation results are shown in Table 4.

Example 17
As resin composition B, PE-B was 99.95 wt%, CAT-1 was 0.05 wt%, PE-B was 99.80 wt%, and CAT-2 was 0.20 wt%. A laminated film was obtained in the same manner as in Example 14 except that. The evaluation results are shown in Table 4.

Example 18
As the resin composition B, instead of 99.95% by weight of PE-B and 0.05% by weight of CAT-1, 99.90% by weight of PE-B and 0.9% of zinc dilaurate (CAT-3) were added. A laminate film was obtained in the same manner as in Example 14 except that the amount was 10% by weight. The evaluation results are shown in Table 4.

Example 19
As resin composition B, instead of 99.95% by weight of PE-B and 0.05% by weight of CAT-1, 99.90% by weight of PE-B and poly {[6- [ (1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4-diyl] [[(2,2,6,6-tetramethyl-4-piperidyl) imino] A laminate film was obtained in the same manner as in Example 14 except that hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]} (CAT-4) was changed to 0.10 wt%. . The evaluation results are shown in Table 4.

Example 20
As resin composition B, instead of 99.95% by weight of PE-B and 0.05% by weight of CAT-1, 99.90% by weight of PE-B and 0% of dimethyl stearate (CAT-5) A laminate film was obtained in the same manner as in Example 14 except that the content was changed to 10% by weight. The evaluation results are shown in Table 4.

Example 21
As the resin composition Ab, 99.80% by weight of PE-A, 0.1% by weight of AS-1, 0.1% by weight of AS-2, 99.70% by weight of PE-A, AS A laminate film was obtained in the same manner as in Example 14 except that -1 was 0.15 wt% and AS-2 was 0.15 wt%. The evaluation results are shown in Table 4.

Example 22
As the resin composition Ab, 99.80% by weight of PE-A, 0.1% by weight of AS-1, 0.1% by weight of AS-2, 99.80% by weight of PE-A, alkyl A laminate film was obtained in the same manner as in Example 14 except that sodium sulfonate (Miyoshi Oil & Fats Co., Ltd., trade name: Dasper 802D, hereinafter sometimes referred to as AS-3) was 0.2% by weight. It was. The evaluation results are shown in Table 4.

Example 23
As resin composition B, instead of 99.95% by weight of PE-B and 0.05% by weight of CAT-1, 99.90% by weight of PE-B, 2-ethyl-zinc hexanoate (CAT-6) A laminate film was obtained in the same manner as in Example 14 except that the content was 0.1 wt%. The evaluation results are shown in Table 4.

Comparative Example 6
Laminated film in the same manner as in Example 14 except that the resin composition B was changed to 99.95% by weight of PE-B and 0.05% by weight of CAT-1 but 100% by weight of PE-B. Got. The evaluation results are shown in Table 5. Both the initial adhesive strength (after 5 minutes) and the adhesive strength after 700 minutes were low and inferior. In addition, in the antistatic property evaluation, a sample subjected to aging treatment for 72 hours in an atmosphere at 40 ° C. was used because of low adhesive strength, but the antistatic property was poor.

Comparative Example 7
As resin composition B, PE-B was changed to 99.95 wt%, CAT-1 was changed to 0.05 wt%, PE-B was changed to 97.80 wt%, and CAT-1 was changed to 2.2 wt%. A laminated film was obtained in the same manner as in Example 14 except that. The evaluation results are shown in Table 5. Both the initial adhesive strength (after 5 minutes) and the adhesive strength after 700 minutes were low and inferior. Moreover, since the adhesive strength did not increase after aging treatment for 72 hours in an atmosphere at 40 ° C., the antistatic property was not evaluated.

Comparative Example 8
As resin composition B, instead of 99.95% by weight of PE-B and 0.05% by weight of CAT-1, 99.90% by weight of PE-B, calcium distearate (manufactured by NOF Corporation) A laminate film was obtained in the same manner as in Example 14 except that the nominal calcium stearate G (hereinafter sometimes referred to as CAT-7) was 0.10% by weight. The evaluation results are shown in Table 5. Both the initial adhesive strength (after 5 minutes) and the adhesive strength after 700 minutes were low and inferior. Moreover, since the adhesive strength was low in the slip property evaluation, a sample which had been subjected to an aging treatment for 72 hours in an atmosphere at 40 ° C. was inferior in antistatic property.

Comparative Example 9
As resin composition Ab, PE-A was changed to 99.80 wt%, AS-1 was changed to 0.1 wt%, AS-2 was changed to 0.1 wt%, and PE-A was changed to 100 wt%. A laminate film was obtained in the same manner as in Example 14. The evaluation results are shown in Table 5, but were inferior in antistatic properties.

Comparative Example 10
As the resin composition Ab, instead of 99.80% by weight of PE-A, 0.1% by weight of AS-1 and 0.1% by weight of AS-2, 97.8% by weight of PE-A, AS Except that -1 was 1.1 wt% and AS-2 was 1.1 wt%, an attempt was made to produce a laminate film in the same manner as in Example 14. However, smoke generation during laminate molding was severe, and the laminate film was Couldn't get.

Example 24
As the olefin polymer, blended so that the propylene polymer (PP) with MFR of 6.5 g / 10 min, density of 900 kg / m ³ is 99.90% by weight, and CAT-2 is 0.10% by weight. Then, it was melt-kneaded with a twin screw extruder (Laboplast Mill manufactured by Toyo Seiki Seisakusho Co., Ltd.) to obtain pellets of resin composition B-1 used for the B layer.

Similarly, PP 99.60% by weight, AS-1 0.2% by weight, polyoxyethylene lauryl amide (manufactured by NOF Corporation, trade name Stahome DL, hereinafter sometimes referred to as AS-4) is 0. The mixture was blended so as to be 2% by weight, and melt-kneaded by a twin screw extruder (Laboplast Mill, manufactured by Toyo Seiki Seisakusho Co., Ltd.) to obtain pellets of the resin composition Ab-4 used for the A layer.

For film molding, a three-type three-layer coextrusion cast film molding machine (manufactured by Plastics Engineering Laboratory) was used. The above resin composition Ab-4 pellets are placed in the extruder constituting one surface layer (A layer), and the resin composition B-1 pellets are placed in the extruder constituting the other two layers (B1 layer, B2 layer). After feeding and extruding from a T-die at a temperature of 220 ° C. to obtain a multilayer film composed of (A) layer / (B1) layer / (B2) layer, the condition of 30 W · min / m ² on the surface of (B2) layer The corona treatment was applied. The thickness of each layer was 20 μm.

Formulation of polyurethane adhesive: Seika Bond E-263 (25 parts) + Seika Bond C-26 (5 parts) + ethyl acetate (150 parts)
Seika Bond is manufactured by Dainichi Seika Kogyo Co., Ltd. Adhesive thickness: 3μm
Table 6 shows the adhesive strength of the obtained laminate film.

Example 25
Instead of the resin composition B-1, an ethylene / 1-hexene copolymer having a MFR of 2 g / 10 min and a density of 920 kg / m ³ (trade name Nipolon Z-ZF230, manufactured by Tosoh Corp., hereinafter referred to as PE -C) may be changed to Resin Composition B-2 with 99.90% by weight and CAT-2 at 0.10% by weight, and PE-C may be used instead of Resin Composition Ab-4. A laminate film was obtained in the same manner as in Example 24 except that the resin composition A-5 was changed to 99.90% by weight, AS-1 0.05% by weight, and AS-2 0.05% by weight. It was.

Table 6 shows the adhesive strength of the obtained laminate film.

Example 26
As resin composition A, PE-A was 99.80 wt%, AS-1 was 0.1 wt%, AS-2 was 0.1 wt%, PE-A was 99.72 wt%, AS A laminate film was obtained in the same manner as in Example 14 except that -1 was changed to 0.10 wt%, AS-2 was changed to 0.10 wt%, and FA-1 was changed to 0.08 wt%. The evaluation results are shown in Table 7.

Example 27
As resin composition B, PE-B was 99.95% by weight, CAT-1 was 0.05% by weight, PE-B was 99.90% by weight, and CAT-2 was 0.10% by weight. A laminated film was obtained in the same manner as in Example 26 except that. The evaluation results are shown in Table 7.

Example 28
As resin composition B, PE-B was 99.95% by weight, CAT-1 was 0.05% by weight, PE-B was 99.90% by weight, and CAT-6 was 0.10% by weight. A laminated film was obtained in the same manner as in Example 26 except that. The evaluation results are shown in Table 7.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.

This application is based on a Japanese patent application filed on April 09, 2009 (Japanese Patent Application No. 2009-094715) and a Japanese patent application filed on April 17, 2009 (Japanese Patent Application No. 2009-1000088). The contents are incorporated herein by reference.

The laminate film of the present invention has excellent adhesiveness without being subjected to an aging treatment and can maintain good slip and antistatic properties for a long period of time. Useful for. Therefore, the industrial value of the present invention is remarkable.

Claims

It is composed of at least four layers of (A) layer / (B) layer / (C) layer / (D) layer, and (A) layer comprises 98 to 99.999% by weight of olefin polymer and 0.001 to 2 fatty acid amide. Resin composition Aa composed of% by weight, (B) layer comprising at least one metal selected from the group consisting of 98 to 99.999% by weight of olefin polymer, zinc, lithium, cobalt, iron, and tin Resin composition B composed of 0.001 to 2% by weight of fatty acid metal salt and / or amine compound, (C) layer is polyurethane-based adhesive and / or isocyanate-based adhesive, and (D) layer is at least one layer A laminate film comprising the above base material.
It is composed of at least four layers of (A) layer / (B) layer / (C) layer / (D) layer, and (A) layer comprises 98 to 99.999% by weight of olefin polymer and 0.001 to 0.001 to antistatic agent. Resin composition Ab comprising 2% by weight, at least one metal selected from the group consisting of 98 to 99.999% by weight of olefin polymer, layer (B), zinc, lithium, cobalt, iron and tin A resin composition B comprising 0.001 to 2% by weight of a fatty acid metal salt and / or an amine compound, wherein the layer (C) is a polyurethane-based adhesive and / or an isocyanate-based adhesive, and the layer (D) is at least 1 A laminate film comprising a substrate of at least layers.
It is composed of at least four layers of (A) layer / (B) layer / (C) layer / (D) layer, and the (A) layer is 96 to 99.998% by weight of olefin polymer and 0.001 to 2 fatty acid amide. Resin composition Ac composed of wt% and antistatic agent 0.001 to 2 wt%, (B) layer is composed of 98 to 99.999 wt% olefin polymer, zinc, lithium, cobalt, iron, and tin A resin composition B composed of 0.001 to 2% by weight of a fatty acid metal salt and / or an amine compound containing at least one metal selected from the group consisting of a polyurethane-based adhesive and / or an isocyanate-based layer An adhesive and a laminate film, wherein the (D) layer comprises at least one base material.
The fatty acid metal salt constituting the resin composition B of the layer (B) is a fatty acid metal salt containing at least one metal selected from the group consisting of zinc, lithium, and cobalt. 4. The laminate film according to any one of 3.
The laminate according to any one of claims 1 to 3, wherein the amine compound constituting the resin composition B of the layer (B) is a polyoxyethylene alkylamine represented by the following general formula (I): the film.

(Wherein R 1 represents a linear or branched alkyl or alkenyl group having 8 to 30 carbon atoms, R 2 and R 3 each independently represents —OCR ′ (R ′ represents a carbon atom having 8 to 30 carbon atoms) Represents a hydrogen group) or -H, and m and n are each independently an integer of 1 to 10.)
4. The laminate film according to claim 1, wherein the amine compound constituting the resin composition B of the (B) layer is a hindered amine light stabilizer.
The laminate film according to any one of claims 1 to 3, wherein the amine compound constituting the resin composition B of the (B) layer is an alkylamine represented by the following general formula (II).

(Wherein R 4 is a linear or branched fatty acid residue having 8 to 30 carbon atoms, R 5 and R 6 are each independently hydrogen, or a linear or branched chain having 1 to 8 carbon atoms. An alkyl group or an alkenyl group.)
The laminate film according to any one of claims 1 to 3, wherein the surface resistivity of the surface on the (A) layer side of the laminate film is 10 13 to 10 17 (Ω).
The laminate film according to any one of claims 1 to 3, wherein the contact angle of water on the (A) layer side surface of the laminate film is from 50 ° to 110 °.
The laminate film according to claim 2 or 3, wherein the antistatic agent constituting the resin composition Ab of the (A) layer or the resin composition Ac contains a glycerin fatty acid ester.
The laminate film according to claim 2 or 3, wherein the antistatic agent constituting the resin composition Ab of the (A) layer or the resin composition Ac contains a polyglycerol fatty acid ester.
The laminate film according to claim 2 or 3, wherein the antistatic agent constituting the resin composition Ab of the (A) layer or the resin composition Ac contains an alkyl sulfonate.
The laminate film according to any one of claims 1 to 3, which has an adhesive strength of 0.7 N / 25 mm or more when left in an atmosphere at 23 ° C for 5 minutes after lamination.