JP2011016232A - Laminate film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate film excellent in adhesiveness just after laminate-molded, capable of shortening an aging treating time for enhancing a curing speed of a polyurethane adhesive, and excellent in slippability.SOLUTION: This laminate film includes at least three layers of a layer (A), a layer (B) and a layer (C), the layer (A) is a resin composition constituted of 98-99.999 wt.% of olefin polymer, and 0.001-2 wt.% of fatty acid metal salt containing at least one kind of metal selected from the group comprising zinc, lithium, cobalt, iron and tin and/or an amine compound, the layer (B) is a polyurethane adhesive comprising a polyol having 200-5,000 of number average molecular weight and an isocyanate compound, and the layer (C) is constituted of at least one layer or more of base material, in the laminate film.

Description

  The present invention relates to a laminate film. More specifically, in a polyurethane adhesive having a low molecular weight such as a solvent-free adhesive, it has excellent adhesiveness immediately after laminate molding without impairing pot life, and it becomes possible to shorten the high-temperature aging treatment time performed after laminate molding, In addition, the present invention relates to a laminate film having high heat seal strength.

  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. In recent years, solvent-free dry laminating methods have attracted attention as a method for producing such a laminate film in accordance with VOC emission regulations against the background of environmental problems. Solventless polyurethane adhesives must have low viscosity in order to perform uniform coating, but polyurethane adhesives using polyols with low molecular weight have poor adhesion between the substrate and the sealant film. Since it is sufficient, the heat seal strength is low, and it has been difficult to use it for packaging of heavy items such as water, packaging materials for boil treatment and retort treatment (see, for example, Patent Documents 1 to 3).

  Moreover, since the molecular weight of the polyol is low, the adhesive strength immediately after the laminate molding is low, and adhesion failure such as tunneling may occur. Further, in order to stabilize the viscosity on the coating roll, the curing reaction is slow, and the aging time is longer than that of the solvent-type polyurethane adhesive.

  In order to solve such problems, a method of modifying the molecular terminal of the polyol with a carboxyl group (for example, see Patent Document 1), a method of adjusting the hydroxyl group concentration of the polyol and the isocyanate group concentration of the isocyanate compound (for example, Patent Documents 2 and 3). A method for improving the adhesive has been proposed. However, although such an adhesive can improve the adhesive strength, it cannot satisfy all of the adhesiveness immediately after molding, the extension of pot life, and the coating ability of the adhesive.

JP-A-8-60131 JP 2003-3145 A JP 2006-213801 A

  The present invention has been made in view of the above situation, and has excellent adhesiveness immediately after laminate molding, and shortens the aging treatment time to increase the curing rate of the polyurethane adhesive without impairing the pot life of the adhesive. An object of the present invention is to provide a laminate film having high heat seal strength.

  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 as an olefin polymer for a laminate film, and thus has a low molecular weight. It has been found that even when a polyurethane-based adhesive using a polyol is used, a laminate film having excellent adhesion immediately after lamination and high heat seal strength can be obtained, and the present invention has been completed.

  That is, the present invention is composed of at least three layers of (A) layer / (B) layer / (C) layer, and (A) layer is 98 to 99.999% by weight of olefin polymer, zinc, lithium, cobalt, A resin composition composed of 0.001 to 2% by weight of a fatty acid metal salt and / or amine compound containing at least one metal selected from iron and tin, (B) a polyol whose layer has a number average molecular weight of 200 to 5000 And a polyurethane adhesive comprising a compound having an isocyanate group, and a laminate film characterized in that the (C) layer comprises at least one substrate.

  The present invention is described in detail below.

  The olefin polymer constituting 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. 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 Propylene-based copolymers such as acid ester copolymers, copolymers of ethylene and acrylic monomers such as ethylene / methacrylate copolymers, polypropylene (PP), propylene / ethylene copolymers, propylene / 1-butene copolymers 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 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 A 1-octene copolymer is preferable, and from the viewpoint of film strength, an ethylene / 1-hexene copolymer, an ethylene / 1-octene copolymer, and a propylene-based polymer are particularly preferable.

  The fatty acid metal salt constituting the present invention contains at least one metal selected from zinc, lithium, cobalt, iron, and tin, and when the metal is zinc, lithium, or cobalt, the curing rate of the adhesive is improved. High effect and preferable. Moreover, you may have 2 or more types of fatty acid from which 1 type or 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, 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 migration of the fatty acid metal salt to the adhesive. When the number of carbon atoms is less than 4, the amount transferred to the polyurethane-based adhesive and / or the isocyanate-based adhesive decreases, and the effect of improving the curing rate of the adhesive is low, which is not preferable. On the other hand, when the number of carbon atoms exceeds 30, the amount of metal atoms decreases, and the effect of improving the curing rate of the adhesive is low, which is not 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 thereof include cobalt, cobalt stearate, dibutyltin oxide, dibutyltin malate, dibutyltin laurate, dioctyltin malate, dioctyltin laurate, iron laurate, and iron stearate. These fatty acid metal salts can be used alone or in combination. Among these fatty acid metal salts, fatty acid zinc salts are preferable because they have a high effect of shortening the aging time, and more preferably carbons of fatty acids such as zinc octoate, zinc octenoate, zinc laurate, and zinc 2-ethylhexanoate. It is the number 8 fatty acid zinc.

  The amine compound constituting 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), a hindered amine light stable An agent and an alkylamine represented by the following general formula (II) are preferred because of excellent adhesion, and a polyoxyethylene alkylamine represented by the following general formula (I) is most preferred. These amine compounds can be used alone or in combination of two or more.

（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。）

(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.)

（式中、Ｒ^４は炭素数が８〜３０である直鎖又は分岐鎖の脂肪酸残基、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若しくはアルケニル基である。）
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、炭素数が８〜３０であり、好ましくは８〜２２である。Ｒ^１、Ｒ^２、Ｒ^３の炭素数が８以上である場合、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量が増大し、接着剤の硬化速度向上効果が高く好ましい。また炭素数が３０以下の場合はアミノ基の量が多くなり、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としては、ドデシルジオキシエチルアミン、テトラデシルジオキシエチルアミン、オクタデシルジオキシエチルアミン、１６−オキシヘプタデシルジオキシエチルアミン、オクタデシルオキシエトキシエチルアミン、１７−オクタデセニルジオキシエチルアミン、１−メチルヘプタデシルジオキシエチルアミンなどを例示することができる。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 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 carbon number 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, and the carbon number of 8 to 30 and preferably 8-22. When R ¹ , R ² , and R ³ have 8 or more carbon atoms, the amount of migration 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, Naimine from NOF Corporation. It is sold under names such as S-210, Naimine O-205, and Naimine T2-202.

  The hindered amine light stabilizer 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-ethanedi ) Bis (3,3,5,5-tetramethylpiperazinone), (mixed 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxyl Rate, (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) undeca ] 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) hexa A condensate of methylenediamine and 1,2-dibromoethane, [N- (2,2,6,6-tetramethyl-4-piperidyl) -2-methyl-2- (2,2,6,6-tetra Methyl-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-piperidi ) 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- [5.1.1.12] -heneicosan-21-one}, 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-dispiro- [5.1.1.12] -Henicosan-21-one, 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-dispiro- [5.1.1.12] -heneicosane And -20-propanoic acid decyl 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 R ⁴ constituting the alkylamine represented by the general formula (II) is important for determining the migration rate of the alkylamine to the adhesive, and preferably has 8 to 30 carbon atoms. More preferably, it is 8-22. When the number of carbon atoms of R ⁴ 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. Moreover, when the carbon number of R ⁵ and R ⁶ is in 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.

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

  The blending ratio in the resin composition constituting the layer (A) of the present invention is 98 to 99.999% by weight of an olefin polymer, and a fatty acid containing at least one metal selected from zinc, lithium, cobalt, iron and tin. Metal salt and / or amine compound 0.001 to 2% by weight, preferably olefin polymer 99 to 99.995% by weight, fatty acid metal containing at least one metal selected from zinc, lithium, cobalt, iron and tin 0.005 to 1% by weight of a salt and / or amine compound, more preferably 99.5 to 99.995% by weight of an olefin polymer, and at least one metal selected from zinc, lithium, cobalt, iron and tin Fatty acid metal salt and / or amine compound 0.005 to 0.5 wt%, most preferably 99.7 to 99.99 wt%, , Lithium, cobalt, iron, 0.01 to 0.3 wt% fatty acid metal salts and / or amine compound containing at least one metal selected from tin. When the fatty acid metal salt and / or amine compound containing at least one metal selected from 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, which is not preferable. When the fatty acid metal salt and / or amine compound containing at least one metal selected from zinc, lithium, cobalt, iron, and tin exceeds 2% by weight, exudation from the laminate film becomes excessive, resulting in a packaging material It is not preferable because the quality of the contents may be impaired.

  In addition, the resin composition constituting the present invention contains additives usually used for olefinic resins such as antioxidants, lubricants, inorganic fillers, surfactants, antistatic agents, slip agents, etc., as necessary. Further, it may be added within a range that does not impair the adhesiveness.

  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.

  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 excellent in flexibility and has few problems such as breakage, so that the thickness is 1 μm to 5 mm. From the viewpoint of economy, the range of 1 to 100 μm is most preferable.

  The (A) layer 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.

  The surface of the (A) layer of the present invention that is in contact with the (B) layer is preferably oxidized in order to increase the curing rate of the adhesive used for the (B) layer and to obtain good adhesive performance.

  (A) Examples of the oxidation treatment method for oxidizing the surface of the layer include chromic acid treatment, sulfuric acid treatment, air oxidation, ozone treatment, corona discharge treatment, flame treatment, plasma treatment, and the like. Corona discharge treatment, flame treatment, plasma treatment, and ozone treatment are particularly preferred for effective formation.

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.

Moreover, when it uses for extrusion lamination molding, in order to acquire favorable adhesiveness, the surface which contact | connects the (B) layer of the (A) 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, and 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-type adhesive which comprises the (B) layer of this invention is comprised from the compound which has a polyol and isocyanate group whose number average molecular weight is 200-5000, Preferably it is 400-4000, More preferably, it is 500-3000.

The number average molecular weight of the polyol is determined by measuring under gel gel permeation chromatography under the following conditions, measuring a universal calibration curve with monodisperse polystyrene, and calculating the molecular weight of polystyrene. When the number average molecular weight is less than 200, it is not preferable because the adhesiveness of the obtained laminate film is poor, and when it exceeds 5000, the viscosity of the adhesive increases and the coating property deteriorates, which is not preferable.
Model: HLC-8120GPC (manufactured by Tosoh Corporation)
Solvent: Tetrahydrofuran Flow rate: 1 mL / min Column temperature: 40 ° C
Measurement concentration: 1 mg / 1 mL
Injection volume: 100 μL
Such a polyol can be appropriately selected from polyester polyols, polyether polyols, polyether ester polyols, polyurethane polyols, acrylic polyols, polyolefin polyols, and the like.

  Examples of polyester polyols include, for example, polycarboxylic acids such as isophthalic acid, terephthalic acid, adipic acid, azelaic acid, sebacic acid or esters thereof, and mixtures thereof, such as ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, Examples thereof include those obtained by reacting glycols such as neopentyl glycol and 1,6-hexanediol or a mixture thereof.

  As examples of polyether polyols, for example, oxirane compounds such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran are polymerized using a low molecular weight polyol such as water, ethylene glycol, propylene glycol, trimethylolpropane, and glycerin as an initiator. What is obtained is mentioned.

  Examples of the polyether ester polyol include those obtained by reacting a polyvalent carboxylic acid such as isophthalic acid, terephthalic acid, adipic acid, azelaic acid, sebacic acid or the like or a mixture thereof with the above polyether polyol. Illustrated.

  Examples of the polyurethane polyol include those obtained by reacting the above-described polyester polyol, polyether polyol, polyether ester polyol and the like with an isocyanate compound described below.

  One or more kinds of such polyols may be used. In addition, polyols having different number average molecular weights can be mixed and used, and the number average molecular weight after mixing plural kinds of polyols may be in the range of 200 to 5,000.

  Isocyanate compounds include 4,4′-, 2,4′- and 2,2′-diisocyanate diphenylmethane, 1,5-diisocyanate naphthalene, 4,4′-diisocyanate dicyclohexylmethane, 1,4-diisocyanatebenzene, and / or Or aromatic diisocyanate 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 Aliphatic and cycloaliphatic diisocyanates such as -3,3,5-trimethyl-3 or -5-isocyanatomethanecyclohexane, isocyanurates, burettes, Bifunctional, trifunctional or higher polyfunctional polyisocyanate compounds such as phanates, or bifunctional polyisocyanate compounds containing terminal isocyanate groups obtained by reaction with bifunctional polyol compounds such as polypropylene glycol, trimethylolpropane, glycerin, etc. Examples thereof include terminal isocyanate group-containing polyfunctional polyisocyanate compounds obtained by reaction with trifunctional or higher functional polyol compounds.

  As such polyurethane adhesives, commercially available products such as those manufactured by Dainichi Seikagaku Co., Ltd., trade names Non-Solbond XC235, Non-Solbond XA129, Non-Solbond XC231, and Non-Solbond XA126 can be used.

  The blending ratio of the polyol and the isocyanate compound is not particularly limited, but the ratio (—OH / NCO) of the hydroxyl group amount (—OH) of the polyroll to the isocyanate group amount (NCO) of the isocyanate compound is 0.1 to 2. It is preferable that it is in the range because of excellent adhesiveness.

  These polyurethane adhesives include reaction promoters, silane coupling agents, titanate coupling agents, aluminum coupling agents, adhesion promoters such as epoxy resins, etc., as long as they do not adversely affect adhesiveness and pot life. Additives can be blended.

  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 polyolefin film with a coater attached to a known extrusion laminator, solvent-type dry laminator, or solvent-free dry laminator. A laminator is most preferred.

  Such polyurethane adhesives can also be used after diluted in a solvent. 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. 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 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 is bonded to the (A) layer and the substrate via the (B) 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.

  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.

  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.

  The laminate film of the present invention is very useful 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 properties for a long period of time. .

  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) Seal strength development time The polyolefin film surfaces of the laminate film obtained according to 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 1-hour intervals for 1 to 16 hours after lamination, and thereafter, from 24 hours to 72 hours at 12-hour intervals. The sample used was left in a 40 ° 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.

(4) Seal strength 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 48 hours after lamination. The sample used was left in a 40 ° 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.

Example 1
As an olefin polymer, an ethylene / 1-hexene copolymer having an MFR of 4 g / 10 min and a density of 923 kg / m ³ (trade name Nipolon Z04P62A manufactured by Tosoh Corp., hereinafter sometimes referred to as PE-A) 99.9% by weight, 2-ethyl-zinc hexanoate (Nippon Chemical Industry Co., Ltd., trade name Nikka Octix zinc 18%, hereinafter sometimes referred to as CAT-1) is blended to 0.1% by weight. Then, it was melt-kneaded with a biaxial extruder (laboroplast mill manufactured by Toyo Seiki Seisakusho Co., Ltd.) to obtain pellets of a resin composition used for the layer (A).

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 (A layer), PE-A is supplied to the extruder constituting the other two layers (B1 layer, B2 layer), and a temperature of 220 ° C. Then, a multilayer film consisting of (A) layer / (B1) layer / (B2) layer was obtained, and the surface of (A) layer was subjected to corona treatment under the condition of 30 W · min / m ² . The thickness of each layer was 20 μm.

  Laminate molding is a ratio shown below at a temperature of 70 ° 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 sometimes referred to as PET). The polyurethane adhesive compounded in (1) was applied with a bar coater, and the film was bonded to the corona-treated surface to obtain a laminate film.

Formulation of polyurethane adhesive: Non-Solbond XC235 (3 parts) + Non-Solbond XA-129 (1 part)
Non-Solbond XC235 (polyol): Number average molecular weight 1100 (manufactured by Dainichi Seika Kogyo Co., Ltd.)
Non-sol bond XA-129 (isocyanate compound): number average molecular weight 1400 (manufactured by Dainichi Seika Kogyo Co., Ltd.)
Adhesive thickness: 1.5 μm
The physical properties of the obtained laminate film are shown in Table 1.

実施例２
樹脂組成物として、ＰＥ−Ａを９９．９重量％、ＣＡＴ−１を０．１重量％の代わりに、ＰＥ−Ａを９９．９５重量％、ＣＡＴ−１を０．０５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 changed to 99.9% by weight, CAT-1 was changed to 0.1% by weight, PE-A was changed to 99.95% by weight, and CAT-1 was changed to 0.05% by weight. Obtained a laminate film in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 3
As the resin composition, PE-A was changed to 99.9% by weight, CAT-1 was changed to 0.1% by weight, PE-A was changed to 99.7% by weight, and CAT-1 was changed to 0.3% by weight. Obtained a laminate film in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 4
As a resin composition, PE-A is 99.9% by weight, CAT-1 is 0.1% by weight, PE-A is 99.9% by weight, zinc dilaurate (manufactured by NOF Corporation) A laminate film was obtained in the same manner as in Example 1 except that the content of zinc claurate (hereinafter sometimes referred to as CAT-2) was 0.1% by weight. The evaluation results are shown in Table 1.

Example 5
As the resin composition, instead of 99.9% by weight of PE-A and 0.1% by weight of CAT-1, 99.9% by weight of PE-A, polyoxyethylene dodecylamine ( A laminate film was obtained in the same manner as in Example 1 except that the product name Nimene L-202 manufactured by NOF Corporation, which may be referred to as CAT-3 hereinafter) was 0.1% by weight. The evaluation results are shown in Table 1.

Example 6
As a resin composition, instead of 99.9% by weight of PE-A and 0.1% by weight of CAT-1, 99.9% by weight of PE-A, dimethyl stearate (manufactured by NOF Corporation) A laminate film was obtained in the same manner as in Example 1 except that 0.1% by weight of name tertiary Nissan amine AB (hereinafter sometimes referred to as CAT-4) was 0.1% by weight. The evaluation results are shown in Table 1.

Comparative Example 1
Example 1 except that the resin composition was PE-A 99.9% by weight, CAT-1 0.1% by weight, PE-A 100% by weight, and CAT-1 was not used. In the same manner, a laminate film was obtained. The evaluation results are shown in Table 1. The seal strength was long and the seal strength was low and inferior.

Comparative Example 2
As the resin composition, PE-A was changed to 99.9% by weight, CAT-1 was changed to 0.1% by weight, PE-A was changed to 97.8% by weight, and CAT-1 was changed to 2.2% by weight. Obtained a laminated film in the same manner as in Example 1. The evaluation results are shown in Table 1. The excess bleed of CAT-1 prolongs the seal strength expression time, and the seal strength is low and inferior.

Example 7
As a resin composition, instead of 99.9% by weight of PE-A and 0.1% by weight of CAT-1, a propylene-based polymer having an MFR of 6.5 g / 10 min and a density of 900 kg / m 3 (Japan) Made by Polypro Co., Ltd., trade name: FW4BT, hereinafter sometimes referred to as PP, 99.9% by weight, CAT-1 at 0.1% by weight, and PP in the (B1) and (B2) layers Except for the use, a laminate film was obtained in the same manner as in Example 1. The evaluation results are shown in Table 2.

比較例３
樹脂組成物として、ＰＰを９９．９重量％、ＣＡＴ−１を０．１重量％の代わりに、ＰＰを１００重量％としＣＡＴ−１を用いなかったこと以外は、実施例７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に示した。シール強度発現時間長いとともに、シール強度が低く劣っていた。

Comparative Example 3
The resin composition was the same as that of Example 7 except that PP was 99.9 wt% and CAT-1 was 0.1 wt%, PP was 100 wt% and CAT-1 was not used. A laminate film was obtained. The evaluation results are shown in Table 2. The seal strength was long and the seal strength was low and inferior.

Comparative Example 4
An attempt was made to produce a laminate film in the same manner as in Example 1 except that Seikadyne A154 (manufactured by Dainichi Seika Kogyo Co., Ltd., number average molecular weight: 9100) from which the solvent was removed by drying was used instead of non-sol bond XC235 as the polyol. However, the viscosity of the adhesive was too high to achieve a coating with a uniform thickness.

Comparative Example 5
An attempt was made to produce a laminate film in the same manner as in Example 1 except that Seikadine E263 (manufactured by Dainichi Seika Kogyo Co., Ltd., number average molecular weight: 8100) from which the solvent was removed by drying instead of non-sol bond XC235 was used as the polyol. However, the viscosity of the adhesive was too high to achieve a coating with a uniform thickness.

Claims (7)

It is composed of at least three layers (A) layer / (B) layer / (C) layer, and the (A) layer is selected from 98 to 99.999% by weight of olefin polymer, zinc, lithium, cobalt, iron, and tin. A resin composition composed of 0.001 to 2% by weight of a fatty acid metal salt and / or an amine compound containing at least one metal, (B) a compound having a polyol and an isocyanate group whose layer has a number average molecular weight of 200 to 5000 A laminate film comprising a polyurethane adhesive comprising: (C) a layer comprising at least one substrate. The laminate film according to claim 1, wherein the fatty acid metal salt is a fatty acid metal salt containing at least one metal selected from zinc, lithium, and cobalt. The laminate film according to claim 1, wherein the fatty acid metal salt is zinc fatty acid derived from a fatty acid having 8 to 22 carbon atoms. The laminate film according to claim 1, wherein the fatty acid metal salt is zinc fatty acid having 8 carbon atoms in the fatty acid. The laminate film according to any one of claims 1 to 4, wherein the amine compound 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 laminate film according to any one of claims 1 to 4, wherein the amine compound 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 laminate film according to any one of claims 1 to 6, wherein the polyurethane adhesive is a solventless adhesive.