JP2013126719A - Method for manufacturing laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a laminate which can manufacture a laminate having excellent interlayer adhesive strength.SOLUTION: The method for manufacturing the laminate includes a step of affixing an anchor coat agent layer (d) surface of a base material (a) having the anchor coat agent layer (d) to a surface not having an anchor coat agent of a base material (b) using an ethylenic polymer (c) at processing temperature higher than 250°C to 340°C with sandwich lamination.

Description

  The present invention relates to a method for manufacturing a laminate.

In general, when a separate attachment member is attached to the surface of the base material, an anchor coat layer may be formed on the surface of the base material in order to activate the surface of the base material.
For example, a base sheet, an isocyanate anchor coat layer coated on the surface of the base sheet, and a polyolefin resin layer laminated via the isocyanate anchor coat layer are provided. A polyolefin-based resin laminate is known (see, for example, Patent Document 1).

Japanese Patent No. 3047126

However, only by forming the anchor coat layer on the substrate, sufficient interlayer adhesion strength may not be obtained when the substrate and the substrate are laminated to produce a laminate.
Therefore, the subject of this invention is providing the manufacturing method of the laminated body which can manufacture the laminated body excellent in interlayer adhesive strength.

Specific means for solving the above problems are as follows.
<1> The surface of the anchor coating agent layer (d) of the substrate (a) having the anchor coating agent layer (d) and the surface of the substrate (b) not having the anchor coating agent exceed 250 ° C. It is a manufacturing method of the laminated body which has the process of carrying out a sandwich lamination process using the ethylene polymer (c) at the processing temperature of 340 degrees C or less, and bonding.
<2> The method for producing a laminate according to <1>, wherein the amount of the anchor coating agent layer (d) is in the range of 0.02 to ² g / m ² .
<3> The sandwich lamination process is a method for producing a laminate according to <1> or <2>, in which a layer having a thickness of 15 μm or less is formed using the ethylene polymer (c).

<4> The ethylene polymer (c) is an ethylene homopolymer, a copolymer of ethylene and another α-olefin, an ethylene-unsaturated carboxylic acid copolymer, an ethylene-unsaturated carboxylic acid ester- Unsaturated carboxylic acid copolymer, ethylene-unsaturated carboxylic acid copolymer ionomer, ethylene-unsaturated carboxylic acid ester-unsaturated carboxylic acid copolymer ionomer, and ethylene-unsaturated carboxylic acid ester copolymer <1> in which the melt flow rate (MFR) is 0.1 to 50 g / min (load 2160 g, temperature 190 ° C.), and the density is 890 to 950 kg / m ^3. It is the manufacturing method of the laminated body as described in any one of-<3>.

<5> The sandwich lamination process forms a layer having a thickness of 7 μm or less using the ethylene polymer (c).
The ethylene polymer (c) is an ethylene-unsaturated carboxylic acid copolymer, an ethylene-unsaturated carboxylic acid ester-unsaturated carboxylic acid copolymer, an ionomer of an ethylene-unsaturated carboxylic acid copolymer, ethylene- It is at least one selected from the group consisting of an unsaturated carboxylic acid ester-unsaturated carboxylic acid copolymer ionomer and an ethylene-unsaturated carboxylic acid ester copolymer, and has a melt flow rate (MFR) of 0.1. to 50 g / min is (load 2160 g, temperature 190 ° C.), a method for producing a density of 890~950kg / ^{m 3} <1> ~ laminate according to any one of <4>.

<6> The substrate (a) is a polyester film, a polyamide film, a polyethylene film, a polypropylene film, a film formed by depositing a metal or an inorganic compound on a polyester film, or a film formed by depositing a metal or an inorganic compound on a polyamide film. Films obtained by vapor-depositing metals or inorganic compounds on polyethylene films, films obtained by vapor-depositing metals or inorganic compounds on polypropylene films, aluminum foils, polyester films having aluminum foil as a surface layer, polyamides having aluminum foil as a surface layer <1> to <5>, which is a film, a polyethylene film having an aluminum foil as a surface layer, or a polypropylene film having an aluminum foil as a surface layer A method for producing a laminate of the mounting.

<7> The substrate (b) is a polyester film, a polyamide film, a polyethylene film, a polypropylene film, a film formed by depositing a metal or an inorganic compound on a polyester film, or a film formed by depositing a metal or an inorganic compound on a polyamide film. Films obtained by vapor-depositing metals or inorganic compounds on polyethylene films, films obtained by vapor-depositing metals or inorganic compounds on polypropylene films, aluminum foils, polyester films having aluminum foil as a surface layer, polyamides having aluminum foil as a surface layer <1> to <6>, which is a film, a polyethylene film having an aluminum foil as a surface layer, or a polypropylene film having an aluminum foil as a surface layer A method for producing a laminate of the mounting.

<8> The laminate according to any one of <1> to <7>, wherein the anchor coating agent layer (d) is a layer formed using a two-component reaction type urethane anchor coating agent. It is a manufacturing method.
<9> When the interlayer adhesive strength between the base material (b) and the layer formed using the ethylene copolymer (c) is measured under a tensile speed of 300 m / min by the T-type peeling method, 3N / It is a manufacturing method of the laminated body as described in any one of <1>-<8> which manufactures the laminated body which is 15 mm or more.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the laminated body which can manufacture the laminated body excellent in interlayer adhesive strength can be provided.

The method for producing a laminate of the present invention comprises a surface of the base material (a) having an anchor coating agent layer (d), the surface of the anchor coating agent layer (d), and a surface of the base material (b) not having an anchor coating agent. A sandwich lamination process using an ethylene polymer (c) at a processing temperature of more than 250 ° C. and 340 ° C. or less (hereinafter also referred to as “sandwich lamination process”), and if necessary It is configured with other processes.
In the sandwich lamination process in the present invention, the base material (a) having the anchor coating agent layer (d) through the ethylene polymer (c) melted so that the resin temperature is higher than 250 ° C. and lower than 340 ° C. And the base material (b) are bonded together, and the base material (a) / anchor coating agent layer (d) / layer using the ethylene polymer (c) (hereinafter referred to as “ethylene polymer (c) ) Layer ”) / substrate (b) is produced. At this time, the anchor coating agent contained in the anchor coating agent layer (d) moves (penetrates) in the ethylene polymer (c) layer, and the ethylene polymer (c) layer and the substrate (b) The interface is reached and, as a result, the bond strength at this interface is improved.
Therefore, according to this invention, the laminated body excellent in interlayer adhesiveness is manufactured.

The sandwich lamination method is not particularly limited and a known method can be used. However, the processing temperature in the sandwich lamination process (resin temperature of the ethylene polymer (c)) exceeds 250 ° C. and 340 It is below ℃.
When the processing temperature is 250 ° C. or lower, the molten film is not stable, and it is generally difficult to process. On the other hand, when the processing temperature exceeds 340 ° C., the resin is severely decomposed and deteriorated, so that it is not suitable for sandwich lamination processing.
The processing temperature is preferably 260 ° C. or higher and 340 ° C. or lower, and more preferably 270 ° C. or higher and 330 ° C. or lower, from the viewpoint of interlayer adhesion strength.

  Further, the processing speed in the sandwich lamination process can be appropriately set within a range usually used, but from the viewpoint of interlayer adhesion strength, 50 to 200 m / min is preferable, 70 to 180 m / min is more preferable, and 100 to 180 m / min is preferable. Minutes are particularly preferred.

The amount of the anchor coating agent layer (d) provided on the substrate (a) is preferably in the range of 0.02 to ² g / m ² .
When the anchor coating agent layer (d) is a layer formed using a coating solution containing an anchor coating agent, the “amount of anchor coating agent layer (d)” is the dry coating amount (solid content coating amount). Means.
When the amount of the anchor coating agent layer (d) is 0.02 g / m ² or more, the amount of movement of the anchor coating agent can be further increased, and the interlayer adhesive strength can be further improved.
When the amount of the anchor coating agent layer (d) is 2 g / m ² or less, the volatilization / drying of the solvent from the coating solution containing the anchor coating agent can be further promoted, and the laminate is more suitable for production.
The amount of anchor coating agent layer (d) is more preferably in the range of 0.04~1g / ^{m 2,} particularly preferably in the range of 0.08~1g / ^{m 2.}

In addition, the thickness of the ethylene polymer (c) layer formed by the sandwich lamination process is not particularly limited, but from the viewpoint of interlayer adhesion strength, weight reduction and resource saving (environmental support). 15 μm or less, more preferably 10 μm or less, and particularly preferably 7 μm or less.
From the viewpoint of interlayer adhesion strength, the thickness of the ethylene polymer (c) layer is preferably 2 μm or more, more preferably 3 μm or more, and particularly preferably 5 μm or more.

  Next, the substrate (a), the substrate (b), the ethylene polymer (c), and the anchor coating agent layer (d) in the present invention will be described.

<Base material (a), base material (b)>
The base material (a) is not particularly limited as long as the base material can be provided with the anchor coating agent layer (d) as a surface layer. For example, various simple films and vapor deposition of metal or inorganic compound as a surface layer. A film having a layer or an aluminum foil, or the like can be used.
More specifically, as the substrate (a), a polyester film, a polyamide film, a polyethylene film, a polypropylene film, a film obtained by depositing a metal or an inorganic compound on a polyester film, or a metal or an inorganic compound is deposited on a polyamide film. Film, polyethylene film deposited metal or inorganic compound film, polypropylene film deposited metal or inorganic compound film, aluminum foil, polyester film having aluminum foil as surface layer, surface foil aluminum foil Polyamide film having an aluminum foil, a polyethylene film having an aluminum foil as a surface layer, a polypropylene film having an aluminum foil as a surface layer, and the like are preferable.

Examples of the polyester constituting the polyester film include polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN). The surface of the polyester film may be subjected to easy adhesion treatment such as coating. The polyester film may be a film having a multilayer structure composed of the above-described plurality of types of polyester.
Examples of the polyamide constituting the polyamide film include nylon-6, nylon-66, and MXD nylon. The surface of the polyamide film may be subjected to easy adhesion treatment such as coating. Further, the polyamide film may have a multilayer structure of the above-described plurality of types of nylon.
Examples of the polyethylene constituting the polyethylene film include high-density polyethylene (HDPE), high-pressure method low-density polyethylene (LDPE), and linear low-density polyethylene (LLDPE). The surface of the polyethylene film may be subjected to easy adhesion treatment such as coating. Further, the polyethylene film may be a multilayer film composed of the above-described plurality of types of polyethylene.
Examples of the polypropylene constituting the polypropylene film include isotactic polypropylene and syndiotactic polypropylene. Moreover, not only a homotype but the random copolymer and block copolymer which are copolymerization with ethylene are mentioned. The surface of the polypropylene film may be subjected to easy adhesion treatment such as coating. The polypropylene film may be a multilayer film composed of the above-described plural types of polypropylene, or a multilayer film composed of one or more types of polypropylene and one or more types of polyethylene.

  As the polyethylene film and the polypropylene film, a stretched film or an unstretched film may be used. However, when heat sealability is required, it is preferable to use an unstretched film.

Moreover, as the base material (a), as described above, a film obtained by depositing a metal or an inorganic compound on a polyester film, a polyamide film, a polyethylene film, or a polypropylene film can be used. Thereby, the barrier property (for example, gas barrier property) of a laminated body can be improved.
Examples of the metal that can be deposited include aluminum. Examples of the inorganic oxide that can be deposited include aluminum oxide (alumina), silicon oxide (silica), magnesium oxide, and tin oxide.

The thickness of the vapor deposition layer made of the metal or the inorganic oxide is preferably in the range of 400 to 3000 mm, although the optimum condition varies depending on the type and configuration of the metal or inorganic oxide used. When the thickness is 400 mm or more, the film forming property and gas barrier property are further improved. When the thickness is 3000 mm or less, damage to the deposited layer due to external factors such as bending and pulling can be further suppressed.
The method for forming these vapor deposition layers is not particularly limited. For example, a vacuum vapor deposition method (for example, resistance heating method, high frequency induction heating method, electron beam heating method, electron impact heating method, flash vapor deposition method, laser vapor deposition method, Etc.), sputtering method, ion plating method and the like.

Moreover, as a film which has aluminum foil as said surface layer, it is using the film formed by laminating aluminum foil as a surface layer with a well-known method with respect to a polyester film, a polyamide film, a polyethylene film, or a polypropylene film. it can. Thereby, the barrier property (for example, gas barrier property) of a laminated body can be improved.
The thickness of the aluminum foil is preferably 2 to 15 μm and more preferably 3 to 10 μm when used as the surface layer.
As thickness of the said aluminum foil, when using as an aluminum foil single-piece | unit, 5-50 micrometers is preferable and 5-30 micrometers is more preferable.

  Although there is no limitation in particular in the thickness of a base material (a), 10-200 micrometers is preferable from a viewpoint of the workability by a sandwich lamination process, 10-100 micrometers is more preferable, and 10-80 micrometers is especially preferable.

The substrate (b) is not particularly limited as long as it is a substrate having a surface not having an anchor coat agent.
As said base material (b), the base material similar to the said base material (a) can be used, for example, A preferable range is also the same.
The preferable thickness of the substrate (b) is the same as the preferable thickness of the substrate (a).

  In the present invention, from the viewpoint of barrier properties (for example, gas barrier properties), at least one of the substrate (a) and the substrate (b) has a metal or inorganic compound vapor-deposited layer or aluminum foil as a surface layer. It is preferable that At this time, the base film on which the surface layer is formed is preferably a polyester film, a polyamide film, a polyethylene film, or a polypropylene film.

When using a film having a metal or inorganic compound vapor-deposited layer or an aluminum foil as the surface layer as the substrate (a), from the viewpoint of more effectively improving the interlayer adhesion, on the vapor-deposited layer or on the aluminum foil It is preferable to provide an anchor coating agent layer (d).
In the case where a film having a metal or inorganic compound vapor-deposited layer or an aluminum foil is used as the surface layer (b), from the viewpoint of more effectively improving the interlayer adhesion, the surface layer side is made of ethylene. The side in contact with the polymer (c) layer is preferred.

<Ethylene polymer (c)>
As the ethylene polymer (c), an ethylene polymer that is usually used for sandwich lamination processing can be used without particular limitation. However, considering the ease of movement of the anchor coating agent and workability in sandwich lamination processing, etc. Are preferably selected.

From the viewpoint of processability, the melt flow rate (MFR) of the ethylene polymer (c) is preferably 0.1 to 50 g / min (load 2160 g, temperature 190 ° C.), preferably 0.5 to 30 g / More preferably, the load is 2160 g (load 2160 g, temperature 190 ° C.).
Here, the melt flow rate (MFR) indicates a melt flow rate measured under the conditions of a load of 2160 g and a temperature of 190 ° C. in accordance with JIS K7210-1999.

The density of the ethylene polymer (c) is preferably 890 to 950 kg / m ³ and more preferably 900 to 945 kg / m ³ from the viewpoint of ease of movement of the anchor coating agent. .

Specific examples of the ethylene polymer (c) include ethylene homopolymers, copolymers of ethylene and other α-olefins, ethylene-unsaturated carboxylic acid copolymers, and ethylene-unsaturated carboxylic acids. Ester-unsaturated carboxylic acid copolymer, ethylene-unsaturated carboxylic acid copolymer ionomer, ethylene-unsaturated carboxylic acid ester-unsaturated carboxylic acid copolymer ionomer, and ethylene-unsaturated carboxylic acid ester copolymer At least one selected from the group consisting of polymers (may be a single type or a mixture of two or more types) is preferred.
When the ethylene-based polymer (c) is a copolymer of ethylene and another monomer, it may be a random copolymer or a block copolymer, but may be a random copolymer. preferable.

(Ethylene homopolymer, copolymer of ethylene and other α-olefin)
Examples of the α-olefin in the copolymer of ethylene and another α-olefin include propylene, butene, hexene, octene and the like.
Examples of the homopolymer of ethylene and the copolymer of ethylene and other α-olefin include, for example, high-density polyethylene (HDPE), high-pressure method low-density polyethylene (LDPE), linear low-density polyethylene ( LLDPE), ethylene / α-olefin copolymer elastomer (ethylene / α-olefin copolymer having a high content of structural units derived from other α-olefins and low crystallinity or substantially no crystallinity) Elastomer).

(Ethylene-unsaturated carboxylic acid copolymer)
Examples of the unsaturated carboxylic acid in the ethylene-unsaturated carboxylic acid copolymer include acrylic acid, methacrylic acid, ethacrylic acid, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, maleic acid, maleic anhydride, maleic acid. Examples thereof include unsaturated carboxylic acids having 3 to 8 carbon atoms or half esters such as acid monoesters (monomethyl maleate, monoethyl maleate, etc.) and maleic anhydride monoesters (monomethyl maleate anhydride, monoethyl maleate anhydride, etc.).
Of these, acrylic acid and methacrylic acid are preferable.

In the ethylene-unsaturated carboxylic acid copolymer, the content of the structural unit derived from the unsaturated carboxylic acid is preferably 1 to 25% by mass, more preferably 2 to 20% by mass.
When the content of the structural unit derived from the unsaturated carboxylic acid is 1% by mass or more, transparency and flexibility are good. Further, when the content ratio of the structural unit derived from the unsaturated carboxylic acid is 25% by mass or less, stickiness, hygroscopicity are suppressed, and workability is good.

In the ethylene-unsaturated carboxylic acid copolymer, other copolymers of more than 0% by mass and 30% by mass or less, preferably more than 0% by mass and 25% by mass or less with respect to 100% by mass in total of ethylene and unsaturated carboxylic acid A structural unit derived from a polymerizable monomer may be contained. Examples of the other copolymerizable monomers include vinyl esters such as vinyl acetate and vinyl propionate, carbon monoxide, glycidyl acrylate, and glycidyl methacrylate.
However, the ethylene-unsaturated carboxylic acid copolymer is preferably a binary copolymer of ethylene and an unsaturated carboxylic acid (preferably a binary random copolymer).

(Ethylene-unsaturated carboxylic acid ester-unsaturated carboxylic acid copolymer)
Examples of the unsaturated carboxylic acid in the ethylene-unsaturated carboxylic acid ester-unsaturated carboxylic acid copolymer are the same as the examples of the unsaturated carboxylic acid in the ethylene-unsaturated carboxylic acid copolymer described above, and are preferable. The range is the same.
Examples of the unsaturated carboxylic acid ester in the ethylene-unsaturated carboxylic acid ester-unsaturated carboxylic acid copolymer include methyl acrylate, ethyl acrylate, isobutyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid. And (meth) acrylic acid esters such as methyl acid and isobutyl methacrylate.
Here, (meth) acrylic acid ester represents acrylic acid ester or methacrylic acid ester.

In the ethylene-unsaturated carboxylic acid ester-unsaturated carboxylic acid copolymer, the content of the structural unit derived from the unsaturated carboxylic acid ester is preferably 2 to 25% by mass, more preferably 6 to 20%. % By mass.
When the content ratio of the structural unit derived from the unsaturated carboxylic acid ester is 2% by mass or more, the permeability (mobility) of the anchor coating agent is increased, and better interlayer adhesion with the base material (b) is further obtained. It becomes easy. Further, when the content ratio of the structural unit derived from the unsaturated carboxylic acid ester is 25% by mass or less, stickiness is suppressed and workability is good.

In the ethylene-unsaturated carboxylic acid ester-unsaturated carboxylic acid copolymer, the content of the structural unit derived from the unsaturated carboxylic acid is preferably 1 to 12% by mass, more preferably 2 to 6% by mass. %.
When the content of the structural unit derived from the unsaturated carboxylic acid is 1% by mass or more, transparency and flexibility are good. Further, when the content ratio of the structural unit derived from the unsaturated carboxylic acid is 12% by mass or less, stickiness is suppressed and workability is good.

In the ethylene-unsaturated carboxylic acid ester-unsaturated carboxylic acid copolymer, more than 0% by mass and 30% by mass or less, preferably 100% by mass in total of ethylene, unsaturated carboxylic acid ester, and unsaturated carboxylic acid. May contain a structural unit derived from 0% by mass to 25% by mass or less of other copolymerizable monomers.
Examples of the other copolymerizable monomers include vinyl esters such as vinyl acetate and vinyl propionate, carbon monoxide, glycidyl acrylate, and glycidyl methacrylate.
However, as the ethylene-unsaturated carboxylic acid ester-unsaturated carboxylic acid copolymer, a terpolymer of ethylene, an unsaturated carboxylic acid ester and an unsaturated carboxylic acid (preferably a ternary random copolymer). Is preferred.

(Ionomer)
As an ionomer of the ethylene-unsaturated carboxylic acid copolymer, the above-mentioned ethylene-unsaturated carboxylic acid copolymer is used as a base polymer, and a part or all of the carboxyl groups contained in the base polymer are crosslinked by metal ions. An ionomer having a different structure can be used.
Further, as an ionomer of an ethylene-unsaturated carboxylic acid ester-unsaturated carboxylic acid copolymer, the above-mentioned ethylene-unsaturated carboxylic acid ester-unsaturated carboxylic acid copolymer is used as a base polymer, and is contained in the base polymer. An ionomer having a structure in which a part or all of the carboxyl groups are crosslinked by metal ions can be used.

  Examples of metal ions contained in the ionomer include monovalent metal ions such as lithium, sodium, potassium, and cesium, divalent metal ions such as magnesium, calcium, strontium, barium, copper, and zinc, and trivalent metals such as aluminum and iron. And ions. The ionomer may contain one kind of metal ion or two or more kinds.

  The degree of neutralization of the unsaturated carboxylic acid in the ionomer is preferably 10 to 80 mol%, more preferably 10 to 70 mol%.

(Ethylene-unsaturated carboxylic acid ester copolymer)
Examples of the unsaturated carboxylic acid ester in the ethylene-unsaturated carboxylic acid ester copolymer include the unsaturated compounds exemplified as the unsaturated carboxylic acid ester in the ethylene-unsaturated carboxylic acid ester-unsaturated carboxylic acid copolymer described above. Carboxylic acid ester is mentioned, The preferable range is also the same.

In the ethylene-unsaturated carboxylic acid ester copolymer, the content of the structural unit derived from the unsaturated carboxylic acid ester is preferably 1 to 25% by mass, more preferably 2 to 20% by mass.
When the content of the structural unit derived from the unsaturated carboxylic acid ester is 1% by mass or more, the transparency and flexibility are excellent, and the permeability (mobility) of the anchor coating agent is increased, and the base material (b) Better interlayer adhesion is more easily obtained. Further, when the content ratio of the structural unit derived from the unsaturated carboxylic acid ester is 25% by mass or less, stickiness is suppressed and the processability is excellent.

Examples of the ethylene polymer (c) include an ethylene-unsaturated carboxylic acid copolymer, an ethylene-unsaturated carboxylic acid ester-unsaturated carboxylic acid copolymer, and an ethylene-unsaturated carboxylic acid from the viewpoint of interlayer adhesion strength. At least one selected from the group consisting of an ionomer of a copolymer, an ionomer of an ethylene-unsaturated carboxylic acid ester-unsaturated carboxylic acid copolymer, and an ethylene-unsaturated carboxylic acid ester copolymer (one type alone) Or may be a mixture of two or more).
Furthermore, a particularly preferred embodiment of the present invention from the viewpoints of interlayer adhesive strength and from the viewpoints of weight reduction and resource saving (environmental support), the ethylene polymer (c) is an ethylene-unsaturated carboxylic acid copolymer. Ethylene-unsaturated carboxylic acid ester-unsaturated carboxylic acid copolymer, ethylene-unsaturated carboxylic acid copolymer ionomer, ethylene-unsaturated carboxylic acid ester-unsaturated carboxylic acid copolymer ionomer, and ethylene -It is at least 1 sort (s) chosen from the group which consists of unsaturated carboxylic acid ester copolymer, Melt flow rate (MFR) is 0.1-50 g / min (load 2160g, temperature 190 degreeC), and a density is 890-. In this embodiment, the thickness is 950 kg / m ³ and the thickness of the layer using the ethylene polymer (c) is 7 μm or less.

<Anchor coating agent layer (d)>
Examples of the anchor coating agent contained in the anchor coating agent layer (d) include a two-component reaction type urethane anchor coating agent, an organic titanate anchor coating agent, a polyethyleneimine anchor coating agent, and a butadiene anchor coating agent. Any known anchor coating agent can be used without particular limitation.
As the anchor coating agent, a two-component reaction type urethane anchor coating agent is particularly preferable from the viewpoint of further promoting the movement (penetration) of the anchor coating agent in the ethylene polymer (c) layer.
Here, the two-component reaction type urethane anchor coating agent is an anchor coating agent in a form used by reacting an isocyanate compound having an isocyanate group at a terminal with a polyol compound having a hydroxyl group at a terminal.
Examples of the isocyanate compound include tolylene diisocyanate, hexamethylene diisocyanate, cyclohexylmethyl diisocyanate, 3,3′-dimethyldiphenylmethane-4,4 ′ diisocyanate, 3,3′-vitrylene-4,4 ′ diisocyanate, and the like. It is done.

The anchor coating agent layer (d) can be formed by applying an anchor coating agent coating solution containing an anchor coating agent on the substrate (a) and drying it. The preferable range of the dry coating amount (solid content coating amount) at this time is as described above.
The anchor coating agent coating solution includes an anchor coating agent (a polyol compound and an isocyanate compound in the case of a two-component reaction type urethane anchor coating agent) and a solvent (for example, ethyl acetate, butyl acetate, toluene, methyl ethyl ketone, etc.) If necessary, it can be prepared by mixing with other components.
The anchor coating agent coating solution can be applied by a known method such as a roll coating method, a die coating method, a knife coating method, a gravure coating method, a dipping method, a spray method, or a screen printing method.

The manufacturing method of the laminated body of this invention may have another process as needed.
In particular, the laminate production method of the present invention preferably has an aging step of performing an aging treatment on the laminate after the above-mentioned sandwich lamination step. By this aging treatment, the movement of the anchor coating agent in the ethylene polymer (c) layer is further promoted, so that the interlayer adhesive strength can be further improved.
Although there is no restriction | limiting in particular in the temperature of an aging process, For example, it can be set as 20 to 80 degreeC, and 30 to 60 degreeC is more preferable.
The aging treatment time can be appropriately set in consideration of the aging treatment temperature, the type of anchor coating agent contained in the anchor coating agent layer (d), the type of ethylene polymer (c), etc. It can be 5 hours to 10 days, and more preferably 12 hours to 3 days.

The laminated body manufactured by the manufacturing method of the laminated body of this invention is excellent in interlayer adhesive strength.
According to the present invention, in the laminate, when the interlayer adhesion strength between the base material (b) and the ethylene copolymer (c) layer is measured by a T-type peeling method under a tensile speed of 300 m / min. For example, it can be set to 3 N / 15 mm or more.
Moreover, the laminated body manufactured by the manufacturing method of the laminated body of this invention can be used for various uses, such as packaging materials, such as a foodstuff, a pharmaceutical, an electronic member, and an electronic device.

Next, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by these examples.
In the following Examples and Comparative Examples, “ac agent” represents an anchor coating agent, “PET” represents polyethylene terephthalate, “CPP” represents unstretched polypropylene, “PE” represents polyethylene, and “LLDPE” Indicates linear low density polyethylene.
Moreover, melt flow rate (MFR) shows the melt flow rate measured based on JISK7210-1999.

<Various films, Al foil>
Details of various films or Al foils used in the following examples and comparative examples are as follows.
-PET film (12 μm thick) “Lumirror P60” (12 μm thick) manufactured by Toray Industries, Inc.
・ PET film (25 μm thickness): “Lumirror P60” (25 μm thickness) manufactured by Toray Industries, Inc.
・ CPP film: Toray Industries, Inc. “Trephan 3517” (30 μm thick)
・ LLDPE film: Mitsui Chemicals Tosero Co., Ltd. “TUX-MCS” (40 μm thickness)
・ Al foil: 7 μm thick aluminum foil manufactured by Sumi Light Aluminum Foil Co., Ltd. ・ Alumina-deposited PET film: “TL-PET-H” (12 μm thickness) manufactured by Mitsui Chemicals, Inc.
・ Silica-deposited PET film: “Tech Barrier H” (12 μm thickness) manufactured by Mitsubishi Plastics, Inc.

<Ethylene copolymer (c)>
In the following examples and comparative examples, the details of the ethylene polymer (A) or the ethylene polymer (B) used as the ethylene copolymer (c) are as follows.
・ Ethylene-based polymer (A): “Mirason 16P” manufactured by Mitsui DuPont Polychemical Co., Ltd. (high pressure method low density polyethylene, MFR = 3.7 g / 10 min, density 923 kg / m ³ )
・ Ethylene polymer (B): Ternary copolymer of ethylene, methacrylic acid and isobutyl acrylate (methacrylic acid content 4% by mass, isobutyl acrylate content 7.5% by mass, MFR = 14 g / 10 min, density 930 kg / m ³ )

<Anchor coat (ac) agent coating solution>
In the following examples, acetic acid coating solution is a two-component mixed ac agent (“Seikadyne 2710A” and “Seikadyne 2710C”) manufactured by Dainichi Seika Kogyo Co., Ltd. and ethyl acetate, Seikadyne 2710A / Seikadyne 2710C / A mixed liquid obtained by mixing at a ratio (mass ratio) of ethyl = 1/2 / 15.5 was used.

<Conditions for sandwich lamination>
Details of the conditions for sandwich lamination in the following examples and comparative examples are as follows.
・ Device: Laminator device manufactured by Sumitomo Heavy Industries Modern Co., Ltd. ・ Extruder: 65 mmφ, L / D = 28
・ Screw: Three stage type (CR = 4.78)
・ Die: 900mm width, inner deckle type ・ Resin temperature (processing temperature): 320 ° C. when using ethylene polymer (A), 315 ° C. when using ethylene polymer (B) (however, In Example 9, 285 ° C.)
・ Processing speed: 120m / min

[Example 1]
<Preparation of base material (b)>
A base material (Al / PE / PET) having a laminated structure of Al / PE / PET was prepared as the base material (b) as follows.
Using the laminator apparatus, an ac agent coating solution is applied onto a PET film (12 μm thick) and dried to obtain a PET film with an ac agent layer, and then the ac agent layer surface of the PET film with an ac agent layer; The Al foil surface was bonded to each other via a molten ethylene polymer (A) (sandwich lamination process) to obtain a substrate (Al / PE / PET). In the base material (Al / PE / PET), the thickness of the layer (PE) formed using the ethylene-based polymer (A) was set to 15 μm.

<Production of Laminate (Base Material (a) / Ac Agent Layer (d) / Ethylene Polymer (c) Layer / Base Material (b))>
Using the laminator apparatus, an ac agent coating solution is applied onto a PET film (12 μm thick) as a substrate (a) so that the dry coating amount is 0.14 g / m ² and dried, and an ac agent layer As a substrate (a) having (d), an ac agent layer-attached PET film is obtained, and then the ac agent layer surface of the ac agent layer-attached PET film and the Al foil surface of the substrate (b), Bonding (sandwich lamination process) through a molten ethylene polymer (A) (corresponding to the above-mentioned “ethylene polymer (c)”), laminate (base material (a) / ac agent layer (d ) / Ethylene polymer (c) layer / substrate (b)). At this time, the thickness of the ethylene polymer (c) layer formed using the ethylene copolymer (A) (ethylene polymer (c)) was set to 10 μm.

<Measurement of interlayer adhesion strength>
The laminate (base (a) / ac agent layer (d) / ethylene polymer (c) layer / base (b)) obtained above was aged under the aging conditions shown in Table 1 below.
After aging, the peeling angle was T-type peeling, and the interlayer adhesion strength (N / 15 mm) at the interface between the substrate (b) and the ethylene copolymer (c) layer was measured under the peeling speed of 300 m / min.
The evaluation results are shown in Table 1.

[Example 2]
In Example 1, a laminate was prepared and interlayer adhesion strength was measured in the same manner as in Example 1 except that the thickness of the ethylene copolymer (c) layer was 15 μm.
The evaluation results are shown in Table 1.

Example 3
In Example 1, except that the type of ethylene copolymer (c), the thickness of the ethylene copolymer (c) layer, the base material (b), and the aging conditions were changed as shown in Table 1 below. In the same manner as in Example 1, the laminate was prepared and the interlayer adhesion strength was measured.
In the production of the laminate, the alumina vapor deposition layer in the base material (b) was in the direction in contact with the ethylene polymer (c) layer.
The evaluation results are shown in Table 1.

Example 4
In Example 3, except that the base material (a), the base material (b), and the aging conditions were changed as shown in Table 1 below, the production of the laminate and the interlayer adhesion strength were changed. Measurements were made.
Here, the base material (PET / PE / Al) as the base material (a) was produced by the same method as the base material (b) in Example 1. Moreover, the ac agent layer was formed on the Al foil side of the base material (PET / PE / Al) as the base material (a).
The evaluation results are shown in Table 1.

Example 5
In Example 4, a laminate was prepared and interlayer adhesion strength was measured in the same manner as in Example 4 except that the dry coating amount of the ac agent coating solution was changed to 0.28 g / m ² .
The evaluation results are shown in Table 1.

Example 6
In Example 1, the base material (a), the type of the ethylene copolymer (c), the thickness of the ethylene copolymer (c) layer, and the base material (b) were changed as shown in Table 1 below. Except that, the laminate was prepared and the interlayer adhesion strength was measured in the same manner as in Example 1.
The evaluation results are shown in Table 1.

[Examples 7 and 8]
Example 1 except that the type of ethylene copolymer (c), the thickness of the ethylene copolymer (c) layer, and the base material (b) were changed as shown in Table 1 in Example 1. In the same manner as described above, the laminate was produced and the interlayer adhesion strength was measured.
The evaluation results are shown in Table 1.

Example 9
In Example 8, the dry coating amount of the ac agent coating solution was changed to 0.42 g / m ² , the thickness of the ethylene copolymer (c) layer was changed as shown in Table 1 below, and the processing temperature was 285. A laminate was prepared and the interlayer adhesion strength was measured in the same manner as in Example 8 except that the temperature was lowered to ° C.
The evaluation results are shown in Table 1.

[Comparative Examples 1-3, 5, and 6]
In Examples 1-3, 6, and 7, instead of the base material (a) having the ac agent layer (d), the side in contact with the ethylene-based copolymer (c) layer without providing the ac agent layer (d) A laminate was prepared and interlayer adhesion strength was measured in the same manner as in Examples 1 to 3, 6 and 7, except that the substrate (a) subjected to corona treatment on the surface of was used.
Here, the corona treatment was performed under the condition of 4 kW using a corona generator type 6090 manufactured by Sophthal.
The evaluation results are shown in Table 1.

[Comparative Example 4]
In Example 4, the base material (a) was changed as shown in Table 1 below, and instead of the base material (a) having the ac agent layer (d), the ac agent layer (d) was not provided and ethylene was used. The laminate was prepared and the interlayer adhesion strength was measured in the same manner as in Example 4 except that the base material (a) subjected to corona treatment on the surface in contact with the system copolymer (c) layer was used. It was.
Here, the corona treatment was performed in the same manner as the corona treatment in Comparative Examples 1 to 3, 5, and 6.
The evaluation results are shown in Table 1.

[Comparative Example 7]
In Example 8, the thickness of the ethylene copolymer (c) layer was changed as shown in Table 1 below, and instead of the base material (a) having the ac agent layer (d), the ac agent layer (d ), And a layered body and interlayer adhesion were obtained in the same manner as in Example 8 except that the substrate (a) subjected to corona treatment on the surface in contact with the ethylene-based copolymer (c) layer was used. Intensity measurements were taken.
Here, the corona treatment was performed in the same manner as the corona treatment in Comparative Examples 1 to 3, 5, and 6.
The evaluation results are shown in Table 1.

<Description of Table 1>
In Table 1, numbers in parentheses after each layer (“12” in PET (12), “10” in ethylene polymer (A) (10), “7” in Al (7), etc.) are The thickness (unit: μm) of each layer is shown.
In Table 1, “non-peelable” indicates that it was not possible to peel at the interface between the base material (b) and the ethylene copolymer (c) layer in the measurement of interlayer adhesive strength. Further, “out of substrate” indicates that the substrate has been cut out in the measurement of the interlayer adhesion strength. Both “not peelable” and “out of substrate” indicate that the interlaminar adhesion strength at the interface between the base material (b) and the ethylene copolymer (c) layer is extremely high.

  As shown in Table 1, the surface of the ac agent layer (d) of the base material (a) having the ac agent layer (d) and the surface of the base material (b) not having the ac agent are divided into an ethylene polymer. The laminates of Examples 1 to 9 obtained by laminating and laminating using (c) were excellent in interlayer adhesive strength at the interface between the base material (b) and the ethylene copolymer (c) layer. .

Claims (9)

  The surface of the anchor coating agent layer (d) of the base material (a) having the anchor coating agent layer (d) and the surface of the base material (b) not having the anchor coating agent exceed 250 ° C. and 340 ° C. or less. The manufacturing method of the laminated body which has the process of carrying out a sandwich lamination process using the ethylene-type polymer (c) at the processing temperature of, and bonding together. The method for producing a laminate according to claim 1, wherein the amount of the anchor coating agent layer (d) is in the range of 0.02 to ² g / m ² .   The said sandwich lamination process is a manufacturing method of the laminated body of Claim 1 or Claim 2 which forms the 15-micrometer-thick layer which uses the said ethylene-type polymer (c). The ethylene polymer (c) is an ethylene homopolymer, a copolymer of ethylene and another α-olefin, an ethylene-unsaturated carboxylic acid copolymer, an ethylene-unsaturated carboxylic acid ester-unsaturated carboxylic acid. The group consisting of an acid copolymer, an ionomer of an ethylene-unsaturated carboxylic acid copolymer, an ionomer of an ethylene-unsaturated carboxylic acid ester-unsaturated carboxylic acid copolymer, and an ethylene-unsaturated carboxylic acid ester copolymer The melt flow rate (MFR) is 0.1 to 50 g / min (load 2160 g, temperature 190 ° C.), and the density is 890 to 950 kg / m ^3. 4. The method for producing a laminate according to any one of 3 above. The sandwich lamination process forms a layer having a thickness of 7 μm or less using the ethylene polymer (c),
The ethylene polymer (c) is an ethylene-unsaturated carboxylic acid copolymer, an ethylene-unsaturated carboxylic acid ester-unsaturated carboxylic acid copolymer, an ionomer of an ethylene-unsaturated carboxylic acid copolymer, ethylene- It is at least one selected from the group consisting of an unsaturated carboxylic acid ester-unsaturated carboxylic acid copolymer ionomer and an ethylene-unsaturated carboxylic acid ester copolymer, and has a melt flow rate (MFR) of 0.1. The method for producing a laminate according to any one of claims 1 to 4, wherein the density is -50 g / min (load 2160 g, temperature 190 ° C), and the density is 890 to 950 kg / m ³ .   The substrate (a) is a polyester film, a polyamide film, a polyethylene film, a polypropylene film, a film formed by depositing a metal or an inorganic compound on a polyester film, a film formed by depositing a metal or an inorganic compound on a polyamide film, a polyethylene film A film formed by depositing a metal or an inorganic compound on a film, a film formed by depositing a metal or an inorganic compound on a polypropylene film, an aluminum foil, a polyester film having an aluminum foil as a surface layer, a polyamide film having an aluminum foil as a surface layer, a surface It is a polyethylene film which has an aluminum foil as a layer, or a polypropylene film which has an aluminum foil as a surface layer, The any one of Claims 1-5. Method for producing a laminate.   The substrate (b) is a polyester film, a polyamide film, a polyethylene film, a polypropylene film, a film formed by depositing a metal or an inorganic compound on a polyester film, a film formed by depositing a metal or an inorganic compound on a polyamide film, a polyethylene film A film formed by depositing a metal or an inorganic compound on a film, a film formed by depositing a metal or an inorganic compound on a polypropylene film, an aluminum foil, a polyester film having an aluminum foil as a surface layer, a polyamide film having an aluminum foil as a surface layer, a surface It is a polyethylene film which has aluminum foil as a layer, or a polypropylene film which has aluminum foil as a surface layer, The any one of Claims 1-6. Method for producing a laminate.   The method for producing a laminate according to any one of claims 1 to 7, wherein the anchor coating agent layer (d) is a layer formed using a two-component reaction type urethane anchor coating agent.   When the interlayer adhesive strength between the base material (b) and the layer formed using the ethylene copolymer (c) is measured under a tensile speed of 300 m / min by the T-type peeling method, it is 3 N / 15 mm or more. The manufacturing method of the laminated body of any one of Claims 1-8 which manufactures a certain laminated body.