JP2010150344A - Resin composition for lamination and laminated film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated film which improves the adhesion immediately after laminate molding without damaging the pot life of a polyurethane adhesive and an isocyanate adhesive. <P>SOLUTION: The resin composition for lamination comprises an olefin polymer, an amine compound having an alkyl group, and a fatty acid metal salt including at least one metal selected from zinc, lithium, cobalt, iron, and tin. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a laminate film. More specifically, the present invention relates to a laminate film having improved adhesiveness immediately after laminate molding without impairing the pot life of the polyurethane adhesive or isocyanate adhesive.

  Laminate films are widely used as a method that enables multifunctional packaging materials such as food packaging, packaging of medical products and medicines, packaging of shampoos and cosmetics, and the like. 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. Moreover, since the adhesive strength immediately after lamination is low due to the slow curing rate, adhesion failure such as tunneling may occur.

  For this reason, a method for increasing the curing rate of the adhesive has been proposed (for example, see Patent Document 1). For example, a method using an isocyanate having a high reaction rate and a method of adding a catalyst for increasing the reaction rate to the adhesive are known. However, there is a problem that a stable coating cannot be performed because the viscosity of the adhesive increases. In particular, since the solventless adhesive cannot reduce the viscosity by the solvent, it is necessary to reduce the viscosity of the adhesive itself, and such a method cannot be selected.

  Further, a method of adding a polyurethane curing catalyst to printing ink has been proposed (see, for example, Patent Document 2). This method is effective as a method for improving the curing rate of the adhesive without changing the viscosity of the adhesive, but in the case where printing is not performed or the pattern where printing ink is not partially present, the curing rate of the portion is increased. It cannot be increased.

  Furthermore, a method of adding a polyurethane curing catalyst to at least one of the films to be bonded has been proposed (see, for example, Patent Document 3), and examples of the catalyst include amine compounds, organotin compounds, epsilon caprolactam, and the like. . However, the amine compound used as a general polyurethane curing catalyst has a low molecular weight like dimethylbenzylamine exemplified in Patent Document 3, and therefore has a large volatilization amount when blended with an olefin resin and formed into a film. There is a high possibility that the moldability is deteriorated and the human body is adversely affected. Moreover, such an amine compound is poor in bleeding to the film surface after blended with an olefin polymer to form a film, and has a small effect of improving the curing rate of the adhesive.

JP-A-8-269428 JP 2000-514376 International Publication No. 97/03821 Pamphlet

  The present invention has been made in view of the situation as described above, and is a laminate excellent in adhesiveness immediately after lamination and excellent in film moldability without requiring an aging treatment for increasing the curing rate of the polyurethane adhesive. The object is to provide a film.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that adhesiveness immediately after lamination is obtained by using a resin composition composed of an olefin polymer, an amine compound having an alkyl group, and a specific fatty acid metal salt. Has been found to be excellent, and the present invention has been completed.

  That is, the present invention comprises at least one metal selected from 96 to 99.998% by weight of an olefin polymer, 0.001 to 2% by weight of an amine compound having an alkyl group, zinc, lithium, cobalt, iron and tin. The present invention relates to a resin composition for laminating comprising 0.001 to 2% by weight of a fatty acid metal salt.

  Further, the present invention comprises at least three layers (A) layer / (B) layer / (C) layer, wherein (A) layer is a polyolefin film comprising the resin composition for lamination, and (B) layer is polyurethane. The present invention relates to a laminate film characterized by comprising a base adhesive and / or an isocyanate adhesive, and (C) a layer comprising at least one substrate.

  The present invention is described in detail below.

  The olefin polymer constituting the resin composition for laminating of the present invention is a homopolymer of a C2-C12 α-olefin such as ethylene, propylene, 1-butene or a copolymer with a vinyl compound. 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 Copolymers, ethylene / vinyl acetate copolymers, ethylene / acrylic acid copolymers, ethylene / methacrylic acid copolymers, ethylene / acrylic acid ester copolymers, ethylene / methacrylic acid ester copolymers, etc. Polymers, polypropylene (PP), propylene-ethylene copolymers, propylene-based polymers such as propylene / 1-butene copolymers, poly-1-butene, poly-1-hexene, poly-4-methyl-1-pentene, etc. These olefin polymers may be used singly or in combination of two or more. Among such olefin-based polymers, because of excellent film moldability and cost performance, low density polyethylene, high density polyethylene, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, ethylene 1-octene copolymer, polypropylene (PP), propylene / ethylene copolymer, and propylene / 1-butene copolymer are preferable. From the viewpoint of film strength, ethylene / 1-hexene copolymer and ethylene / 1-octene are preferable. A copolymer is particularly preferred.

The olefin polymer constituting the present invention preferably has a density measured in accordance with JIS K6922-1 (1997) in the range of 880 to 970 kg / m ³ because a laminate film suitable for packaging materials can be obtained. . If the density is too low, the heat resistance of the film may be insufficient. If the density is too high, the rigidity of the film may be too high.

  The amine compound having an alkyl group constituting the present invention is a compound containing one or more alkyl groups and one or more amino groups in the molecule. Such compounds include alkylamines, alkyldiamines such as oleylpropylenediamine, stearylpropylenediamine, polyoxyethylenealkylamines such as polyoxyethylenealkylamines, polyoxyethylene laurylpropylenediamine, and polyoxyethylenestearylpropylenediamine. Examples include diamines. Such amine compounds having an alkyl group may be used alone or in combination of two or more.

  Among these, polyoxyethylene alkylamines represented by the following general formula (I) are particularly preferable because they are excellent in the effect of increasing the curing rate of the adhesive.

（式中、Ｒ_１は炭素数８〜３０の直鎖又は分岐鎖のアルキル基又はアルケニル基を示し、Ｒ_２、Ｒ_３は−ＯＣＲ′（Ｒ′は炭素数８〜３０の炭化水素基を表す）又は−Ｈを表し、ｍ、ｎは１〜１０の整数である。）
このようなポリオキシエチレンアルキルアミンを構成するＲ_１、Ｒ_２、Ｒ_３の炭素数は、該ポリオキシエチレンアルキルアミンの接着剤への移行速度を決定するため重要であり、好ましくは炭素数が８〜３０であり、更に好ましくは８〜２２である。Ｒ_１、Ｒ_２、Ｒ_３の炭素数がこの範囲にあると、ポリウレタン系接着剤及び／又はイソシアネート系接着剤への移行性に優れ、接着剤の硬化速度向上効果が高く好ましい。このようなポリオキシエチレンアルキルアミンは一種を単独で用いても構わないが、二種以上を混合して使用してもよい。

(In the formula, R ₁ represents a linear or branched alkyl or alkenyl group having 8 to 30 carbon atoms, R ₂ and R ₃ represent —OCR ′ (R ′ represents a hydrocarbon group having 8 to 30 carbon atoms, Or -H, and m and n are integers of 1 to 10.)
The number of carbon atoms of R ₁ , R ₂ and R ₃ constituting such a polyoxyethylene alkylamine is important for determining the migration rate of the polyoxyethylene alkylamine to the adhesive, It is 8-30, More preferably, it is 8-22. When the number of carbon atoms of R ₁ , R ₂ , and R ₃ is within this range, the transition to a polyurethane-based adhesive and / or an isocyanate-based adhesive is excellent, and the effect of improving the curing rate of the adhesive is high. Such polyoxyethylene alkylamines may be used singly or in combination of two or more.

  Examples of such polyoxyethylene alkylamines include N-hydroxyethyl laurylamine, polyoxyethylene laurylamine, polyoxyethylene stearylamine, polyoxyethylene oleylamine, and the like. 201, Nymeen L-202, Nymeen L-207, Nymeen S-202, Nymeen S-204, Nymeen S-210, Nymeen O-205, Nymeen T2-202, and the like.

  Moreover, since the amine compound which has an alkyl group is an alkylamine represented by the following general formula (II), since it is excellent in the effect which raises the cure rate of an adhesive agent, it is preferable.

（式中、Ｒ_４は炭素数が８〜３０である直鎖又は分岐鎖のアルキル基、Ｒ_５およびＲ_６は水素、又は炭素数が１〜８である直鎖若しくは分岐鎖のアルキル基又は若しくはアルケニル基である。）
このようなアルキルアミンを構成するＲ_４基の炭素数は、該アルキルアミンの接着剤への移行速度を決定するため重要であり、好ましくは炭素数が８〜３０であり、更に好ましくは８〜２２である。Ｒ_４基の炭素数がこの範囲にあると、ポリウレタン系接着剤及び／又はイソシアネート系接着剤への移行性に優れ、接着剤の硬化速度向上効果が高く好ましい。また、Ｒ_５，Ｒ_６基の炭素数がこの範囲にあると接着剤の硬化速度向上効果が高く好ましい。このようなアルキルアミンは一種を単独で用いても構わないが、二種以上を混合して使用してもよい。

(Wherein R ₄ is a linear or branched alkyl group having 8 to 30 carbon atoms, R ₅ and R ₆ are hydrogen, or a linear or branched alkyl group having 1 to 8 carbon atoms, or Or an alkenyl group.)
The carbon number of the R ₄ group constituting such an alkylamine is important for determining the migration rate of the alkylamine to the adhesive, and preferably has 8 to 30 carbon atoms, more preferably 8 to 22. When the number of carbon atoms in the R ₄ group is within this range, it is preferable that the transition to polyurethane adhesive and / or isocyanate adhesive is excellent, and the effect of improving the curing rate of the adhesive is high. In addition, when the number of carbon atoms in the R ₅ and R ₆ groups is within this range, the effect of improving the curing rate of the adhesive is high and 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.

  The fatty acid metal salt constituting the present invention is characterized by containing at least one metal selected from zinc, lithium, cobalt, iron, and tin. When the metal is zinc, the effect of improving the curing rate of the adhesive is high and preferable. . Moreover, you may have 1 type, or 2 or more types of fatty acid from which chain length and a structure differ in 1 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, and most preferably 12 to 18 carbon atoms. Control of the fatty acid chain length is important because it determines the rate of migration of the fatty acid metal salt to the adhesive. When the number of carbon atoms is 4 or more, the amount of migration to a polyurethane-based adhesive and / or an isocyanate-based adhesive is improved, and the effect of improving the curing rate of the adhesive is high and preferable. Moreover, when carbon number is 30 or less, the quantity of a metal atom increases and the hardening rate improvement effect of an adhesive agent is high and preferable. Such fatty acid metal salts include zinc monooctanoate, zinc dioctanoate, zinc monooctenoate, zinc dioctenoate, zinc monolaurate, zinc dilaurate, zinc monostearate, zinc distearate, zinc behenate, 2-ethyl. Examples include zinc hexanoate, lithium octanoate, lithium laurate, lithium stearate, cobalt naphthenate, cobalt stearate, iron laurate, iron stearate, dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin dimercapto, dioctyltin malate, etc. can do.

  Such fatty acid metal salts can be obtained from commercial products. Fatty acid zinc is sold under the trade names such as zinc claurate and zinc stearate from NOF Corporation. The fatty acid lithium is sold by, for example, Kawamura Kasei Kogyo Co., Ltd. Fatty acid tin is sold by ADEKA Corporation.

  The blending ratio in the resin composition constituting the present invention is selected from 96 to 99.998% by weight of an olefin polymer, 0.001 to 2% by weight of an amine compound having an alkyl group, zinc, lithium, cobalt, iron and tin. The fatty acid metal salt containing at least one kind of metal is 0.001 to 2% by weight, preferably 98 to 99.988% by weight of the olefin polymer, 0.002 to 1% by weight of the amine compound, and the fatty acid metal salt. 0.01 to 1% by weight, more preferably 99.3 to 99.988% by weight of the olefin polymer, 0.002 to 0.2% by weight of the amine compound, and 0.01 to 0.3% of the fatty acid metal salt. 5% by weight, more preferably 99.4 to 99.985% by weight of the olefin polymer. When the amine compound is less than 0.001% by weight, the effect of improving the curing rate of the adhesive is low, which is not preferable. When the amine compound exceeds 2% by weight, exudation from the laminate film becomes excessive, and the packaging material and In such a case, the quality of the contents may be impaired. Moreover, when the fatty acid metal salt is less than 0.001% by weight, the effect of improving the curing rate of the adhesive is low, which is not preferable. When the fatty acid metal salt exceeds 2% by weight, exudation from the laminate film becomes excessive. In the case of a packaging material, the quality of the contents may be impaired, which is not preferable.

  In addition, the resin composition constituting the present invention may have additives such as antioxidants, lubricants, anti-blocking agents, surfactants, slip agents, and the like that are usually used in olefin resins, if necessary. You may add in the range which does not impair.

  The resin composition constituting 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 using a melt-kneading apparatus, the melting temperature is preferably about the melting point of the olefin polymer to about 350 ° C.

  Using the resin composition of the present invention, a polyolefin film 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 thickness of the polyolefin film constituting the present invention is not particularly limited as long as the object of the present invention is achieved, and is preferably 1 μm to 5 mm in thickness because of excellent flexibility and small problems such as breakage. From the viewpoint of economy, the range of 1 μm to 100 μm is most preferable.

  In order that the polyolefin film surface of this invention may raise the cure rate of the adhesive agent used for (B) layer, and obtain favorable adhesive performance, it is preferable that the adhesive surface which contact | connects the adhesive agent of (B) layer is oxidized.

  Examples of oxidation treatment methods for oxidizing the polyolefin film surface include chromic acid treatment, sulfuric acid treatment, air oxidation, ozone treatment, corona discharge treatment, flame treatment, and plasma treatment. Therefore, corona discharge treatment, flame treatment, plasma treatment, and ozone treatment are particularly preferable.

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, propane, or the like 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.

In addition, when subjected to extrusion lamination molding, in order to obtain good adhesion, at least the surface in contact with the substrate of the molten film made of the resin composition for extrusion lamination of the present invention extruded from the die is air-oxidized or ozone Oxidation by treatment is possible. 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 isocyanate adhesive constituting the layer (B) of the present invention are not particularly limited, and known ones can be used.

  As polyurethane 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., as isocyanate adhesives, Commercial products such as Coronate L manufactured by Nippon Polyurethane Industry Co., Ltd. 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.

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

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

  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 solvent-free 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.

  As a base material which comprises the (C) layer of this invention, a synthetic polymer film or sheet, a woven fabric, a nonwoven fabric, paper, metal foil, etc. are mentioned. 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 fabric and 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.

  The laminate film of the present invention is composed of three layers (A) layer / (B) layer / (C) layer, and includes other layers on the surface of (A) layer or on the surface of (C) layer. May be.

  The laminate film of the present invention can be produced by laminating a polyolefin film and a substrate using a known extrusion laminate molding machine, solvent-type dry laminate molding machine, solventless dry laminate molding machine, or the like.

  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 appropriately 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.

  In addition, 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.

Further, the laminate film of the present invention preferably has a surface resistivity value of (A) layer side surface in the range of 10 ¹³ to 10 ¹⁷ (Ω) because it can suppress a decrease in adhesive strength over time. ¹⁴ to 10 ¹⁷ (Ω) is more preferable. In addition, the measurement of the surface specific resistance value uses TR8601 and TR-42 manufactured by Advantest Co., Ltd., and the specific resistance value 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. A laminate film satisfying this range can be suitably obtained by controlling the compounding ratio of the amine compound having an alkyl group and the fatty acid metal salt, the thickness of the polyolefin film, and the coating amount of the polyurethane adhesive.

  Furthermore, the laminate film of the present invention is preferably such that the contact angle of water on the (A) layer-side surface is 50 ° or more and 110 ° or less because a decrease in adhesive strength over time can be suppressed. In addition, a contact angle is obtained by calculating | requiring the value immediately after dripping pure water on the (A) layer surface. A laminate film satisfying this range can be suitably obtained by controlling the compounding ratio of the amine compound having an alkyl group and the fatty acid metal salt, the thickness of the polyolefin film, and the coating amount of the polyurethane adhesive.

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

  Since the laminate film of the present invention is excellent in adhesiveness even without being subjected to an aging treatment, it is very useful as a packaging film for foods having excellent productivity.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

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

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

(3) Adhesion Adhesion between a PET film and a polyolefin film obtained by cutting the laminate film obtained in the example into a shape having a width of 25 mm and a length of 100 mm and bonding the laminate film via a polyurethane adhesive and / or an isocyanate adhesive. The strength 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.

(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 an autograph DCS-100 (manufactured by Shimadzu Corporation). The measurement was performed at intervals of 1 hour for 1 to 12 hours after lamination, and thereafter at intervals of 12 hours until 72 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 specific resistance value Using a TR8601 and TR-42 manufactured by Advantest Co., Ltd., in an environment of 23 ° C. and 50% RH, the laminate film obtained by the example after 1 minute at an applied voltage of 500 kV (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., in an environment of 23 ° C. and 50% RH, (A ) The contact angle immediately after dropping pure water on the layer side surface was determined.

Example 1
Low-density polyethylene (trade name Petrocene 213 manufactured by Tosoh Corp., hereinafter referred to as PE-A) having an MFR of 8 g / 10 min and a density of 918 kg / m ³ as an olefin polymer 99.94% by weight In addition, 0.01% by weight of polyoxyethylene laurylamine (trade name: Naimine L-202 manufactured by NOF Corporation, hereinafter may be referred to as B-1) as an amine compound having an alkyl group, stearin as a fatty acid metal salt Zinc acid (trade name zinc stearate manufactured by NOF Corporation, hereinafter referred to as C-1) may be mixed to 0.05%, and a twin screw extruder (Toyo Seiki Seisakusho Lab. The resin composition pellets were obtained by melt-kneading with a plast mill).

  The obtained pellets were supplied to an extruder of an extrusion laminating apparatus (made by Placo Corporation) having a screw of 25 mmΦ, and a polyolefin film that was air oxidized by extruding from a T die at a temperature of 320 ° C. Polyurethane blended in the ratio shown below on the corona-treated surface of a biaxially stretched polyamide film (trade name ester film N-1100 manufactured by Toyobo Co., Ltd., thickness 25 μm, hereinafter sometimes referred to as PET) The resin is applied between a base material coated with an adhesive and the solvent dried and a polyethylene film (trade name LIX-1, manufactured by Toyobo Co., Ltd., thickness 40 μm) which is a thermoplastic resin film fed from the second paper feeding unit. The composition was extruded and laminated to a thickness of 20 μm to obtain a laminate film.

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 1 shows the adhesive strength of the obtained laminate film.

実施例２
樹脂組成物として、ＰＥ−Ａを９９．９４重量％、Ｂ−１を０．０１重量％、Ｃ−１を０．０５重量％とした代わりに、ＰＥ−Ａを９９．８８重量％、Ｂ−１を０．０２重量％、Ｃ−１を０．１重量％とした以外は、実施例１と同様にしてラミネートフィルムを得た。評価結果を表１に示した。

Example 2
As a resin composition, PE-A was 99.94% by weight, B-1 was 0.01% by weight, and C-1 was 0.05% by weight. A laminate film was obtained in the same manner as in Example 1 except that -1 was changed to 0.02 wt% and C-1 was changed to 0.1 wt%. The evaluation results are shown in Table 1.

Example 3
Instead of 99.94 wt% PE-A, 0.01 wt% B-1 and 0.05 wt% C-1 as the resin composition, 99.68 wt% PE-A, B A laminate film was obtained in the same manner as in Example 1 except that -1 was changed to 0.02 wt% and C-1 was changed to 0.3 wt%. The evaluation results are shown in Table 1.

Example 4
As a resin composition, PE-A was 99.94% by weight, B-1 was 0.01% by weight, and C-1 was 0.05% by weight. A laminate film was obtained in the same manner as in Example 1 except that -1 was 0.05% by weight and C-1 was 0.05% by weight. The evaluation results are shown in Table 1.

Example 5
As a resin composition, instead of PE-A, an ethylene / 1-hexene copolymer having an MFR of 10 g / 10 min and a density of 914 kg / m ³ as an olefin polymer (trade name Nipolon, manufactured by Tosoh Corporation) A laminate film was obtained in the same manner as in Example 2 except that Z-TZ420 (hereinafter sometimes referred to as PE-B) was used. The evaluation results are shown in Table 1.

Example 6
As a resin composition, instead of B-1, polyoxyethylene stearylamine (trade name Naimine S-202 manufactured by NOF Corporation, hereinafter referred to as B-2) may be used as an amine compound having an alkyl group. A laminate film was obtained in the same manner as Example 2 except that it was used. The evaluation results are shown in Table 1.

Example 7
As the resin composition, dimethylstearylamine (trade name tertiary amine AB manufactured by NOF Corporation, hereinafter may be referred to as B-3) was used as an amine compound having an alkyl group instead of B-1. Except for this, a laminate film was obtained in the same manner as in Example 2. The evaluation results are shown in Table 1.

Example 8
Implementation was performed except that dioctyltin dilaurate (trade name OT-1, manufactured by ADEKA Co., Ltd., hereinafter sometimes referred to as C-2) was used as the fatty acid metal salt instead of C-1 as the resin composition. A laminate film was obtained in the same manner as in Example 2. The evaluation results are shown in Table 1.

Comparative Example 1
As a resin composition, PE-A was changed to 99.94% by weight, B-1 was changed to 0.01% by weight, and C-1 was changed to 0.05% by weight. A laminate film was obtained in the same manner as in Example 1 except that 1 and C-1 were not blended. The evaluation results are shown in Table 2, but both the adhesiveness and the seal strength expression time were inferior.

比較例２
樹脂組成物として、ＰＥ−Ａを９９．９４重量％、Ｂ−１を０．０１重量％、Ｃ−１を０．０５重量％とした代わりに、ＰＥ−Ａを９９．９８重量％、Ｂ−１を０．０２重量％とし、Ｃ−１を配合しなかったこと以外は、実施例１と同様にしてラミネートフィルムを得た。評価結果を表２に示すが、接着性は優れるものの、シール強度発現時間が劣っていた。

Comparative Example 2
Instead of 99.94 wt% PE-A, 0.01 wt% B-1 and 0.05 wt% C-1 as the resin composition, 99.98 wt% PE-A, B A laminate film was obtained in the same manner as in Example 1 except that -1 was 0.02% by weight and C-1 was not blended. The evaluation results are shown in Table 2. Although the adhesiveness was excellent, the seal strength expression time was inferior.

Comparative Example 3
Instead of 99.94 wt% PE-A, 0.01 wt% B-1 and 0.05 wt% C-1, the resin composition was 99.90 wt% PE-A, C -1 was 0.1 wt%, and a laminate film was obtained in the same manner as in Example 1 except that B-1 was not blended. The evaluation results are shown in Table 2, but both the adhesiveness and the seal strength expression time were inferior.

Comparative Example 4
Instead of 99.94 wt% PE-A, 0.01 wt% B-1 and 0.05 wt% C-1, the resin composition was 95.6 wt% PE-A, B A laminate film was obtained in the same manner as in Example 1 except that -1 was changed to 2.2 wt% and C-1 was changed to 2.2 wt%. The evaluation results are shown in Table 2, but both the adhesiveness and the seal strength expression time were inferior.

Example 9
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 .88 wt%, B-1 is 0.02 wt%, C-1 is 0.1 wt%, and melt kneaded with a twin screw extruder (laboroplast mill manufactured by Toyo Seiki Seisakusho Co., Ltd.) A pellet of the resin composition 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 pellets are supplied to an extruder constituting one surface layer (A1 layer), and PP (100% by weight) pellets are supplied to an extruder constituting the other two layers (A2 layer, A3 layer). After extruding from a T-die at a temperature of 220 ° C. to obtain a multilayer film composed of (A1) layer / (A2) layer / (A3) layer, the corona was formed on the surface of (A1) layer under the condition of 30 W · min / m ^2. Treated. The thickness of each layer was 20 μm.

  For the laminate molding, a solvent-type dry laminator (manufactured by Inoue Metal Industry Co., Ltd.) was used. A polyurethane adhesive compounded in the ratio shown below is applied to the corona-treated surface of a biaxially stretched polyamide film (trade name ester film N-1100, manufactured by Toyobo Co., Ltd., thickness 25 μm, hereinafter sometimes referred to as Ny). 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 manufactured by Dainichi Seika Kogyo Co., Ltd. Adhesive thickness: 3μm
The adhesive strength of the obtained laminate film is shown in Table 2.

Example 10
As the olefin polymer used in the (A1) layer, 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 Corporation) In some cases, a laminate film was obtained in the same manner as in Example 9, except that the PP of the (A1) layer and the (A2) layer was changed to PE-C.

Claims (7)

Fatty acid metal salt containing 96 to 99.998% by weight of an olefin polymer, 0.001 to 2% by weight of an amine compound having an alkyl group, and at least one metal selected from zinc, lithium, cobalt, iron and tin. A laminating resin composition comprising 001 to 2% by weight. The resin composition for a laminate according to claim 1, wherein the amine compound having an alkyl group is a polyoxyethylene alkylamine represented by the following general formula (I).

(In the formula, R ₁ represents a linear or branched alkyl or alkenyl group having 8 to 30 carbon atoms, R ₂ and R ₃ represent —OCR ′ (R ′ represents a hydrocarbon group having 8 to 30 carbon atoms, Or -H, and m and n are integers of 1 to 10.) The resin composition for laminate according to claim 1, wherein the amine compound having an alkyl group is an alkylamine represented by the following general formula (II).

(In the formula, R ₄ is a linear or branched fatty acid residue having 8 to 30 carbon atoms, R ₅ and R ₆ are hydrogen, or a linear or branched alkyl group having 1 to 8 carbon atoms. Or an alkenyl group.) The resin composition for lamination according to claim 1, wherein the fatty acid metal salt is a zinc salt of a higher fatty acid having 4 to 30 carbon atoms. A polyolefin film comprising at least three layers of (A) layer / (B) layer / (C) layer, wherein the (A) layer comprises the resin composition for laminate according to claim 1, and the (B) layer A polyurethane-based adhesive and / or an isocyanate-based adhesive, (C) a laminate film comprising a substrate having at least one layer. The laminate film according to claim 5, 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 claim 6 or 7, wherein a contact angle of water on the surface on the (A) layer side of the laminate film is 50 ° or more and 110 ° or less.