WO2019117085A1

WO2019117085A1 - Layered body

Info

Publication number: WO2019117085A1
Application number: PCT/JP2018/045317
Authority: WO
Inventors: 礒川　素朗; 佳那福山; 中野　重則; 久夫五戸; 博樹 ▲高▼岡
Original assignee: 三井・デュポンポリケミカル株式会社
Priority date: 2017-12-15
Filing date: 2018-12-10
Publication date: 2019-06-20
Also published as: JPWO2019117085A1

Abstract

This layered body (10) is provided with a thermoplastic polyurethane resin layer (A), an ionomer resin layer (B), and an adhesive resin layer (C) disposed between the thermoplastic polyurethane resin layer (A) and the ionomer resin layer (B). The adhesive resin layer (C) comprises an adhesive resin composition that includes: at least one ethylene/polar monomer copolymer (C1) chosen from the group consisting of ethylene/vinyl ester copolymers and ethylene/unsaturated carboxylic acid ester copolymers; and an ethylene-based copolymer (C2) that contains a glycidyl group (other than the ethylene/polar monomer copolymer (C1)).

Description

Laminate

The present invention relates to a laminate.

Thermoplastic polyurethane resins have been used in a wide variety of fields and applications as representative thermoplastic elastomers because they have both rubber-like, flexible elasticity and toughness like hard plastics.

By laminating the thermoplastic polyurethane resin layer on another resin layer, for example, while maintaining the elasticity and toughness of the thermoplastic polyurethane resin, it is possible to improve the adhesiveness, the handling property, etc. which are the weak points of the thermoplastic polyurethane resin. A polyurethane-based multilayer film is produced.

As a technique regarding a polyurethane-type multilayer film, the thing of patent document 1 is mentioned, for example.
Patent Document 1 discloses a thermoplastic polyurethane resin layer (A), an ethylene-vinyl acetate copolymer layer (B) having a vinyl acetate content of 7 to 35% by weight, a polyethylene resin layer, or a polypropylene resin layer ( A polyurethane-based multilayer film is described in which C) is laminated in this order. Here, in Patent Document 1, the resin layer (C) is finally peeled off from the thermoplastic polyurethane resin layer (A). That is, in Patent Document 1, the ethylene-vinyl acetate copolymer layer (B) is not provided for the purpose of improving the interlayer adhesion strength between the thermoplastic polyurethane resin layer (A) and the resin layer (C). .

JP-A-8-230119

Since the thermoplastic polyurethane resin is an expensive resin, it is possible to reduce the amount of thermoplastic polyurethane resin used while maintaining excellent properties such as flexibility, mechanical strength, transparency and the like possessed by the thermoplastic polyurethane resin film. The body is sought.
Further, according to the study of the present inventors, it has been revealed that the conventional thermoplastic polyurethane resin film may be difficult to remove the dirt adhering to the surface, and is inferior in the staining resistance.
That is, the present inventors have improved the resistance to staining while maintaining the characteristics of flexibility, mechanical strength and transparency possessed by the thermoplastic polyurethane resin layer in the conventional thermoplastic polyurethane resin film, and further the heat resistance. It has been found that there is room for improvement in terms of relatively reducing the amount of use of the flexible polyurethane resin layer.

The present invention has been made in view of the above circumstances, and is excellent in balance of flexibility, mechanical strength, transparency, interlayer adhesion and stain resistance, and can reduce the amount of thermoplastic polyurethane resin used. It provides a laminate.

The present inventors diligently studied to achieve the above object. As a result, by laminating the ionomer resin layer to the thermoplastic polyurethane resin layer via the specific adhesive resin layer, flexibility, mechanical strength and transparency are reduced while reducing the amount of the thermoplastic polyurethane resin layer used. It has been found that the performance balance of the properties, interlayer adhesion and stain resistance can be improved, and the present invention has been achieved.

That is, according to the present invention, the following laminate is provided.

[1]
Thermoplastic polyurethane resin layer (A), ionomer resin layer (B), adhesive resin layer (C) provided between the thermoplastic polyurethane resin layer (A) and the ionomer resin layer (B) And a laminate comprising
The adhesive resin layer (C) comprises at least one ethylene / polar monomer copolymer (C1) selected from ethylene / vinyl ester copolymer and ethylene / unsaturated carboxylic acid ester copolymer, and glycidyl group-containing A laminate comprising an adhesive resin composition comprising an ethylene-based copolymer (C2) (but excluding the ethylene / polar monomer copolymer (C1)).
[2]
In the laminate according to the above [1],
The adhesive resin composition comprises an ethylene / polar monomer copolymer (C3) modified with a silane coupling agent (with the proviso that the ethylene / polar monomer copolymer (C1) and the glycidyl group-containing ethylene copolymer (C3) A laminate further including C2).
[3]
In the laminate according to the above [2],
The ethylene / polar monomer copolymer (C3) is a laminate comprising an ethylene / vinyl acetate copolymer.
[4]
In the laminate according to the above [2] or [3],
The silane coupling agent in the modification of the ethylene / polar monomer copolymer (C3) comprises a silane coupling agent having a polymerizable group, a silane coupling agent having an amino group, and a silane coupling agent having an epoxy group. A laminate comprising one or more selected from the group.
[5]
In the laminate according to any one of the above [1] to [4],
The laminated body by which at least one part of the said glycidyl group containing ethylene-based copolymer (C2) is modified | denatured by the silane coupling agent.
[6]
In the laminate according to the above [5],
The silane coupling agent in the modification of the glycidyl group-containing ethylene copolymer (C2) is a silane coupling agent having a polymerizable group, a silane coupling agent having an amino group, and a silane coupling agent having an epoxy group. A laminate comprising one or more selected from the group consisting of
[7]
In the laminate according to any one of the above [1] to [6],
The laminated body in which the said ionomer resin layer (B) contains the ionomer of an ethylene and unsaturated carboxylic acid-type copolymer.
[8]
In the laminate according to any one of the above [1] to [7],
A laminate having a mass ratio of the content of the ethylene / polar monomer copolymer (C1) to the content of the glycidyl group-containing ethylene copolymer (C2) in the adhesive resin composition of 1 or more and 30 or less .
[9]
In the laminate according to any one of the above [1] to [8],
The above glycidyl group-containing ethylene copolymer (C2) is ethylene / (meth) acrylate glycidyl copolymer, ethylene / (meth) acrylate glycidyl / vinyl acetate copolymer, and ethylene / (meth) acrylate glycidyl The laminated body containing 1 type, or 2 or more types selected from the group which consists of a (meth) acrylic acid ester copolymer.
[10]
In the laminate according to any one of the above [1] to [9],
A laminate wherein the ethylene / polar monomer copolymer (C1) contains an ethylene / vinyl acetate copolymer.
[11]
In the laminate according to any one of the above [1] to [10],
A laminate having a stress at break of 20 MPa or more measured in accordance with JIS K 6781: 1994.
[12]
In the laminate according to any one of the above [1] to [11],
A laminate having an elongation between marked lines of 100% or more measured in accordance with JIS K6781: 1994.
[13]
In the laminate according to any one of the above [1] to [12],
Laminated body whose Haze measured based on JISK7136: 2000 is 5% or less.
[14]
In the laminate according to any one of the above [1] to [13],
A laminate having a total light transmittance of 80% or more measured in accordance with JIS K7136: 2000.
[15]
In the laminate according to any one of the above [1] to [14],
A laminate having an interlayer adhesion strength of 1.0 N / 15 mm or more between the thermoplastic polyurethane resin layer (A) and the ionomer resin layer (B), which is measured in accordance with JIS Z1707: 1997.
[16]
In the laminate according to any one of the above [1] to [15],
The laminated body further equipped with an adhesive layer (D) in any one outermost layer.
[17]
In the laminate according to the above [16],
The pressure-sensitive adhesive layer (D) is composed of at least one pressure-sensitive adhesive selected from urethane pressure-sensitive adhesives, rubber pressure-sensitive adhesives, silicone pressure-sensitive adhesives, styrenic pressure-sensitive adhesives, olefinic pressure-sensitive adhesives and acrylic pressure-sensitive adhesives Stacks.
[18]
In the laminate according to any one of the above [1] to [17],
A laminate selected from the group consisting of a protective film, a pressure resistant hose, a fuel tube, a multilayer tube, a film for clothing, a film for treating body fluid, a medical tape, a waterproof sheet for building materials, an antifouling tape, a repair tape and a masking tape.
[19]
In the laminate according to any one of the above [1] to [17],
A laminate that is a paint protection film.
[20]
In the laminate according to any one of the above [1] to [19],
The laminated body used so that the said ionomer resin layer (B) surface may become an air | atmosphere side.

ADVANTAGE OF THE INVENTION According to this invention, it is excellent in the performance balance of a softness | flexibility, mechanical strength, transparency, interlayer adhesiveness, and stain resistance, and can provide the laminated body which can reduce the usage-amount of a thermoplastic polyurethane resin layer. .

The objects described above, and other objects, features and advantages will become more apparent from the preferred embodiments described below and the following drawings associated therewith.

It is a sectional view showing typically an example of structure of a layered product of an embodiment concerning the present invention.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. Unless otherwise noted, “X to Y” in the numerical range represents X or more and Y or less. Also, in the present embodiment, "(meth) acrylic" means acrylic, methacrylic or both acrylic and methacrylic.

1. Laminate FIG. 1 is a cross-sectional view schematically showing an example of the structure of a laminate 10 according to an embodiment of the present invention.
The laminate 10 according to this embodiment is provided between the thermoplastic polyurethane resin layer (A), the ionomer resin layer (B), and the thermoplastic polyurethane resin layer (A) and the ionomer resin layer (B). And an adhesive resin layer (C). The adhesive resin layer (C) comprises at least one ethylene / polar monomer copolymer (C1) selected from ethylene / vinyl ester copolymer and ethylene / unsaturated carboxylic acid ester copolymer, and glycidyl group-containing ethylene It is comprised by the adhesive resin composition containing the type | system | group copolymer (C2) (however, except ethylene and a polar monomer copolymer (C1)).

According to the laminate 10 of the present embodiment, the thermoplastic polyurethane resin layer (A) and the ionomer resin layer (B) provide excellent scratch resistance and resistance to the ionomer resin layer (B). Chipping property and stain resistance can be provided. Furthermore, by laminating the thermoplastic polyurethane resin layer (A) and the ionomer resin layer (B) via the adhesive resin layer (C), the thermoplastic polyurethane resin layer (A) and the ionomer resin layer (B) Between the thermoplastic polyurethane resin layer (A) and the thermoplastic polyurethane resin layer (C), even if the amount of the thermoplastic polyurethane resin layer (A) used is reduced. By the adhered ionomer resin layer (B), it is possible to suppress the decrease in flexibility, mechanical strength and transparency of the thermoplastic polyurethane resin layer (A).
From the above, the laminate 10 according to the present embodiment is excellent in performance balance of flexibility, mechanical strength, transparency, interlayer adhesion, and stain resistance, and the amount of the thermoplastic polyurethane resin layer (A) used It can be reduced.

In the thermoplastic polyurethane resin layer (A), a layer containing a thermoplastic polyurethane resin as a main component is preferably constituted by a single layer, but a plurality of thermoplastic polyurethane resins different in kind, content, etc. It may be composed of layers.
In addition, "main component" means that a thermoplastic polyurethane resin contains 50 mass% or more in a thermoplastic polyurethane resin layer (A).

Further, in the ionomer resin layer (B), although it is preferable that the layer containing the ionomer resin as a main component is constituted by a single layer, it is constituted by a plurality of layers different in kind, content etc. of the ionomer resin It may be
The term "main component" means that the ionomer resin is contained in an amount of 50% by mass or more in the ionomer resin layer (B).

In the present embodiment, the total thickness of the laminate 10 is preferably 10 μm or more and 1000 μm or less, more preferably 30 μm or less, from the viewpoint of performance balance of flexibility, mechanical strength, transparency, interlayer adhesion, and stain resistance. Or more and 500 μm or less.

In the laminate 10 according to the present embodiment, the thickness (a) of the thermoplastic polyurethane resin layer (A) is preferable from the viewpoint of the balance of performance in flexibility, mechanical strength, transparency, interlayer adhesion, and stain resistance. The thickness (b) of the ionomer resin layer (B) is preferably 3 μm to 800 μm, more preferably 10 μm to 500 μm, and the adhesive resin layer (b) is preferably 3 μm to 800 μm, more preferably 10 μm to 500 μm. The thickness (c) of C) is preferably 3 μm or more and 200 μm or less, more preferably 10 μm or more and 100 μm or less.

The ratio (a / c) of the thickness (a) of the thermoplastic polyurethane resin layer (A) to the thickness (c) of the adhesive resin layer (C) is preferably 2/1 or more and 50/3 or less. When a / c is in the above range, the performance balance of mechanical strength and interlayer adhesion can be further improved.
The ratio (c / b) of the thickness (c) of the adhesive resin layer (C) to the thickness (b) of the ionomer resin layer (B) is preferably 3/20 or more and 3/5 or less. When c / b is in the above range, the mechanical strength can be improved while the amount of the thermoplastic polyurethane resin layer used is further reduced.

In the laminate 10 according to the present embodiment, the stress at break measured according to JIS K 6781: 1994 is preferably 20 MPa or more, more preferably 25 MPa or more, and particularly preferably 30 MPa or more. .
When the stress at break is equal to or more than the above lower limit value, mechanical strength such as toughness of the laminate 10 can be further improved. The upper limit of the stress at break of the laminate 10 is not particularly limited, and is, for example, 100 MPa or less. In order to achieve such a stress at break, the compositions and types of the thermoplastic polyurethane resin layer (A), the ionomer resin layer (B) and the adhesive resin layer (C), the thickness of each layer, etc. may be appropriately adjusted. Good. Here, the stress at break of the laminate 10 according to the present embodiment can be, for example, an average value of stress at break in the MD direction and stress at break in the TD direction.

In the laminate 10 according to this embodiment, the elongation between marks measured according to JIS K 6781: 1994 is preferably 100% or more, more preferably 200% or more, and 300% or more. Is more preferable, and 400% or more is particularly preferable.
The flexibility of the laminated body 10 can be made still more favorable as elongation between benchmarks is more than the said lower limit. The upper limit value of the elongation between marked lines of the laminate 10 is not particularly limited, and is, for example, 1000% or less. In order to achieve such an elongation between marks, the composition and type of the thermoplastic polyurethane resin layer (A), the ionomer resin layer (B) and the adhesive resin layer (C), the thickness of each layer, etc. Just do it. Here, for the elongation between marked lines of the laminate 10 according to the present embodiment, for example, an average value of the elongation between marked lines in the MD direction and the elongation between marked lines in the TD direction can be adopted.

The stress at break and the elongation between marking lines of the laminate 10 are measured using a tensile tester in accordance with JIS K 6781: 1994. The measurement can be performed by cutting the laminate 10 into a size of No. 1 dumbbell as a test piece, and pulling under the conditions of a distance between chucks of 90 mm and a tensile speed of 50 mm / min. In addition, the said tensile test is performed in 23 degreeC and the environment of 50% of a relative humidity. The elongation between marks represents the elongation immediately before breakage between the determined reference points of the test piece (laminated body 10) in the tensile test. The stress at break is a value obtained by dividing the tensile force at break at the time of breakage in a tensile test by the initial cross-sectional area of the test piece.

In the laminate 10 according to this embodiment, the interlayer adhesive strength between the thermoplastic polyurethane resin layer (A) and the ionomer resin layer (B) measured according to JIS Z1707: 1997 is 1.0 N / 15 mm or more. Is preferably 2.0 N / 15 mm or more, and more preferably 3.0 N / 15 mm or more.
The interlayer adhesiveness of the thermoplastic polyurethane resin layer (A) and the ionomer resin layer (B) in the laminate 10 can be further improved as the interlayer adhesive strength is at least the above lower limit value. Although the upper limit of the said interlayer adhesion strength of the laminated body 10 is not specifically limited, For example, it is 20 N / 15 mm or less. In order to achieve such interlayer adhesion strength, the composition and type of the thermoplastic polyurethane resin layer (A), ionomer resin layer (B) and adhesive resin layer (C), type of each layer, thickness, etc. are appropriately adjusted. do it.

In the laminate 10 according to this embodiment, the haze measured in accordance with JIS K 7136: 2000 is preferably 5% or less, more preferably 4% or less, and particularly preferably 3% or less. preferable. Although the lower limit of the above-mentioned Haze of layered product 10 is not limited in particular, for example, it is 0% or more.
Thereby, the transparency of the laminate 10 can be further improved.

In the laminate 10 according to the present embodiment, the total light transmittance measured according to JIS K 7136: 2000 is preferably 80% or more, more preferably 85% or more, and 90% or more. Is particularly preferred. The upper limit of the total light transmittance of the laminate 10 is not particularly limited, and is, for example, 100% or less.
Thereby, the transparency of the laminate 10 can be further improved.

In addition, the laminate 10 according to the present embodiment may be composed only of the thermoplastic polyurethane resin layer (A), the adhesive resin layer (C) and the ionomer resin layer (B), and various kinds of laminates 10 can be used. Layer (A), adhesive resin layer (C), and layers other than ionomer resin layer (B) (hereinafter also referred to as other layers) from the viewpoint of imparting You may have on the surface side of (A) and / or an ionomer resin layer (B). Examples of other layers include a base material layer, an inorganic layer, a gas barrier layer, an antistatic layer, a hard coat layer, an adhesive layer, an antireflective layer, an antifouling layer, a sealant layer, an undercoat layer, and an adhesive layer. Can. The other layer may have one layer alone or may have two or more layers in combination.

Although the shape of the laminated body 10 which concerns on this embodiment is not specifically limited, For example, a film, a tube hose, a tape, a sheet | seat, etc. are mentioned.
The laminate 10 according to the present embodiment is not particularly limited, but, for example, a protective film, a pressure-resistant hose, a fuel tube, a multilayer tube, a film for clothing, a film for treating body fluid, a medical tape, a waterproof sheet for building materials, an antifouling tape, It can be suitably used as at least one selected from the group consisting of a repair tape and a masking tape.
Among these, the laminate 10 according to the present embodiment can be particularly suitably used as a protective film.
The protective film is, for example, a paint protection film (PPF) that protects the body of an automobile, aircraft, ship, etc. from stone splashing and scratches, etc. Electronic film to be attached to the surface of electronic components such as light guide plate, polarization plate, retardation plate Protective films for parts; protective films for protecting surfaces of synthetic resin plates, decorative plates, metal plates and the like; protective films for protecting surfaces of windows, construction materials, digital signage, packaging, office supplies, medical equipment and the like.

When using the laminated body 10 which concerns on this embodiment as a protective film, it is preferable that the laminated body 10 is further equipped with an adhesive layer (D) in any one outermost layer. From the viewpoint of improving the stain resistance of the laminate 10, the pressure-sensitive adhesive layer (D) is preferably provided as the outermost layer on the thermoplastic polyurethane resin layer (A) side, but is not limited thereto.
The pressure-sensitive adhesive layer (D) can be formed, for example, by applying a pressure-sensitive adhesive to the thermoplastic polyurethane resin layer (A) side or the ionomer resin layer (B) side. It may be formed directly on the surface of the resin layer, or may be laminated via another layer with the resin layer.
The pressure-sensitive adhesive used for the pressure-sensitive adhesive layer is not particularly limited, and examples thereof include acrylic pressure-sensitive adhesives, rubber pressure-sensitive adhesives, urethane pressure-sensitive adhesives, silicone pressure-sensitive adhesives, styrene pressure-sensitive adhesives, and olefin pressure-sensitive adhesives. Acrylic pressure-sensitive adhesives are preferable from the viewpoint of being excellent in heat resistance and weather resistance.
The layer thickness of the pressure-sensitive adhesive layer (D) can be, for example, 3 to 100 μm, preferably 5 to 50 μm, and more preferably 10 to 30 μm.
The layer in contact with the pressure-sensitive adhesive layer (D) can be subjected to surface treatment such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, application of an undercoat, and the like.

When the laminate of this embodiment is used, the thermoplastic polyurethane resin layer (A) surface may be on the air side (the side exposed to the air), or even if the ionomer resin layer (B) surface is on the air side. Although it is good, it is preferable to use so that an ionomer resin layer (B) surface may be on the air side from a viewpoint of improving stain resistance.

Hereinafter, each layer which comprises the laminated body 10 is demonstrated.

<Thermoplastic polyurethane resin layer (A)>
The thermoplastic polyurethane resin layer (A) contains a thermoplastic polyurethane resin as a main component.
The content of the thermoplastic polyurethane resin in the thermoplastic polyurethane resin layer (A) according to the present embodiment is preferably 50% by mass or more, more preferably 100% by mass of the entire thermoplastic polyurethane resin layer (A). The content is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more. When the content of the thermoplastic polyurethane resin in the thermoplastic polyurethane resin layer (A) according to the present embodiment is equal to or more than the above lower limit value, balance of performance such as transparency, flexibility and mechanical strength of the laminate 10 can be obtained. It can be made even better.
Although the upper limit of content of the thermoplastic polyurethane resin in the thermoplastic polyurethane resin layer (A) which concerns on this embodiment is not specifically limited, For example, it is 100 mass% or less.

The thermoplastic polyurethane resin which comprises a thermoplastic polyurethane resin layer (A) is not specifically limited, A well-known thing can be used. For example, block copolymers having a polyurethane as a hard segment and a polyester such as an adipate-based polyester, a caprolactone-based polyester, and a polycarbonate as a soft segment can be mentioned.

More specifically, the thermoplastic polyurethane resin constituting the thermoplastic polyurethane resin layer (A) is formed of a difunctional polyol, a diisocyanate, and a chain extender, and contains a urethane group in its molecular structure. The resin etc. which have thermoplasticity among resin are mentioned.

The thermoplastic polyurethane resin is a block copolymer comprising a hard segment formed by the reaction of a chain extender and a diisocyanate, and a soft segment formed by the reaction of a difunctional polyol and a diisocyanate. preferable.

The thermoplastic polyurethane resin is classified according to the type of the raw material difunctional polyol and the like, and examples thereof include polyether thermoplastic polyurethane resins, polyester thermoplastic polyurethane resins, and polycarbonate thermoplastic polyurethane resins. These thermoplastic polyurethane resins may be used alone or in combination of two or more.

The difunctional polyol is not particularly limited, and examples thereof include polyether polyols, polyester polyols, polycarbonate polyols and the like.
One of these difunctional polyols may be used alone, or two or more thereof may be used in combination.

Examples of the polyether-based polyol include polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol and the like. These polyether-based polyols include polycondensation of 1,2-ethanediol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, etc., ethylene oxide, propylene oxide, tetrahydrofuran etc. These compounds can be obtained by ring-opening polymerization of cyclic ethers of
Examples of the above-mentioned polyester-based polyols include polyester polyols obtained by polycondensation of a dibasic acid such as adipic acid, sebacic acid and terephthalic acid with a low molecular weight polyol, and polycaprolactone glycol.
Examples of the polycarbonate-based polyol include polycarbonate polyols obtained by polycondensation of a low molecular weight polyol with dialkyl carbonates such as dimethyl carbonate and diethyl carbonate, phosgene, chloroformate, diallyl carbonate, alkylene carbonate and the like. .

Examples of the diisocyanate include toluene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), polymeric MDI, tolylene diisocyanate, p-phenylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate hydrogenated MDI and the like. It can be mentioned.

Examples of the chain extender include polyoxyethylene glycol, polyoxypropylene glycol, 1,4-butanediol, trimethylolpropane, bishydroxyethoxybenzene and the like.

Various additives can be contained in the thermoplastic polyurethane resin layer (A) which concerns on this embodiment in the range which does not impair the objective of the present invention. Although various additives are not particularly limited, for example, plasticizers, antioxidants, ultraviolet absorbers, wavelength converting agents, antistatic agents, surfactants, coloring agents, light stabilizers, foaming agents, lubricants, crystal nuclei Agents, crystallization accelerators, crystallization retarders, catalyst deactivators, heat ray absorbents, heat ray reflectors, heat radiating agents, thermoplastic resins other than ionomer resins, thermosetting resins, inorganic fillers, organic fillers, resistance Impact modifiers, slip agents, crosslinkers, crosslinking aids, tackifiers, silane coupling agents, processing aids, mold release agents, hydrolysis inhibitors, heat resistant stabilizers, anti blocking agents, antifogging agents, hard A flame retardant, a flame retardant auxiliary agent, a light diffusing agent, an antibacterial agent, a mildew-proof agent, a dispersing agent, other resin etc. can be mentioned. The various additives may be used singly or in combination of two or more.

<Ionomer resin layer (B)>
The ionomer resin layer (B) contains an ionomer resin as a main component.
As the ionomer resin, an ionomer of an ethylene / unsaturated carboxylic acid copolymer is preferable.
The ionomer of the ethylene-unsaturated carboxylic acid copolymer according to the present embodiment is an ionomer of a polymer obtained by copolymerizing ethylene and at least one of unsaturated carboxylic acids, and an ethylene-unsaturated carboxylic acid-based co-polymer It is a resin in which at least a part of carboxyl groups of the polymer is neutralized with metal ions.
As the ethylene-unsaturated carboxylic acid copolymer, a copolymer containing ethylene and an unsaturated carboxylic acid can be exemplified.

In the ionomer of the ethylene / unsaturated carboxylic acid copolymer according to the present embodiment, the constituent unit derived from ethylene when the total of the constituent units constituting the ethylene / unsaturated carboxylic acid copolymer is 100% by mass. Is preferably 65% by mass to 95% by mass, more preferably 75% by mass to 92% by mass, and the constituent unit derived from the unsaturated carboxylic acid is preferably 5% by mass to 35% by mass, more preferably Preferably they are 8 mass% or more and 25 mass% or less.
The heat resistance, mechanical strength, processability, etc. of the laminate 10 can be further improved when the structural unit derived from ethylene is at least the above lower limit value. Moreover, transparency, a softness | flexibility, interlayer adhesiveness, etc. of the laminated body 10 can be made more favorable for the structural unit derived | led-out from ethylene being below the said upper limit.
When the structural unit derived from the unsaturated carboxylic acid is at least the above lower limit, the transparency, the flexibility, the interlayer adhesion and the like of the laminate 10 can be further improved. Moreover, the heat resistance, mechanical strength, processability, etc. of the laminated body 10 can be made more favorable as the structural unit derived | led-out from unsaturated carboxylic acid is below the said upper limit.

Examples of the unsaturated carboxylic acid constituting the ionomer of the ethylene-unsaturated carboxylic acid copolymer according to the present embodiment include acrylic acid, methacrylic acid, 2-ethyl acrylic acid, crotonic acid, maleic acid, fumaric acid, Itaconic acid, maleic anhydride, fumaric anhydride, itaconic anhydride, monomethyl maleate, monoethyl maleate and the like can be mentioned.
Among these, it is preferable that the above-mentioned unsaturated carboxylic acid contains at least one selected from acrylic acid and methacrylic acid from the viewpoint of productivity and hygienicity of an ionomer of ethylene / unsaturated carboxylic acid copolymer. These unsaturated carboxylic acids may be used alone or in combination of two or more. In addition, an ethylene-unsaturated carboxylic acid-based one containing one or more of the above-mentioned unsaturated carboxylic acids such as acrylic acid and methacrylic acid as constituent units in an ionomer of one or more ethylene-unsaturated carboxylic acid-based copolymers. A copolymer can be added to make an ionomer of an ethylene / unsaturated carboxylic acid copolymer.
In the present embodiment, a particularly preferred ethylene / unsaturated carboxylic acid copolymer is an ethylene / (meth) acrylic acid copolymer.

The ionomer of the ethylene / unsaturated carboxylic acid copolymer preferably contains 0% by mass or more and 30% or less, based on 100% by mass of all the constituent units constituting the ionomer of the ethylene / unsaturated carboxylic acid copolymer. A constituent unit derived from other copolymerizable monomers of mass% or less, more preferably 0% by mass or more and 25% by mass or less may be included. Other copolymerizable monomers include unsaturated esters, for example, vinyl esters such as vinyl acetate and vinyl propionate; methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, (meth) acrylic And (meth) acrylic acid esters such as n-butyl acid and 2-ethylhexyl (meth) acrylate. It is preferable in the point which the softness | flexibility of the laminated body 10 improves that the structural | constituent unit derived | led-out from another copolymer monomer is contained in the said range.

Examples of metal ions constituting the ionomer of the ethylene / unsaturated carboxylic acid type copolymer according to the present embodiment include lithium ions, potassium ions, sodium ions, silver ions, mercury ions, copper ions, and other monovalent metal ions; calcium Ions, magnesium ions, zinc ions, aluminum ions, barium ions, beryllium ions, strontium ions, copper ions, cadmium ions, mercury ions, tin ions, lead ions, iron ions, iron ions, cobalt ions, nickel ions, etc. Can be mentioned.
Among these, lithium ion, potassium ion, sodium ion, calcium ion, magnesium ion, zinc ion, aluminum ion, and barium ion are preferably selected from one or more selected from potassium ion, sodium ion, zinc ion And at least one selected from magnesium ions is more preferable, and it is particularly preferable to include at least one selected from sodium ions and zinc ions.

The degree of neutralization of the ionomer of the ethylene / unsaturated carboxylic acid copolymer according to the present embodiment is not particularly limited, but from the viewpoint of making the flexibility, adhesiveness, mechanical strength, processability, etc. of the laminate 10 better. Therefore, 95% or less is preferable, 90% or less is more preferable, 80% or less is more preferable, 70% or less is still more preferable, and 60% or less is particularly preferable.
The degree of neutralization of the ionomer of the ethylene / unsaturated carboxylic acid copolymer according to this embodiment is not particularly limited, but from the viewpoint of making the transparency, heat resistance, water resistance, etc. of the laminate 10 better, 5% or more is preferable, 10% or more is more preferable, 15% or more is more preferable, and 20% or more is particularly preferable.
Here, the degree of neutralization of the ionomer of the ethylene / unsaturated carboxylic acid copolymer is determined by the carboxyl being neutralized by the metal ion among all the carboxyl groups contained in the ethylene / unsaturated carboxylic acid copolymer. Refers to the percentage of groups.

The method for producing the ethylene-unsaturated carboxylic acid copolymer that constitutes the ionomer of the ethylene-unsaturated carboxylic acid copolymer according to the present embodiment is not particularly limited, and can be produced by a known method. For example, it can be obtained by radical copolymerization of each polymerization component under high temperature and high pressure. Further, the ionomer of the ethylene-unsaturated carboxylic acid copolymer according to the present embodiment can be obtained by reacting an ethylene-unsaturated carboxylic acid copolymer with a metal compound. In addition, as the ionomer of the ethylene / unsaturated carboxylic acid copolymer, those commercially available may be used.

In this embodiment, the melt mass flow rate (MFR) of the ionomer of the ethylene / unsaturated carboxylic acid copolymer, which is measured under the conditions of 190 ° C. and 2160 g load according to JIS K 7210: 1999, is 0.01 g / m. It is preferably 10 minutes to 50 g / 10 minutes, more preferably 0.1 g / 10 minutes to 30 g / 10 minutes, and particularly preferably 0.1 g / 10 minutes to 10 g / 10 minutes. preferable. When the MFR is at least the above lower limit, the processability of the ionomer of the ethylene / unsaturated carboxylic acid copolymer can be further improved. The heat resistance of the laminated body 10 obtained as MFR is below the said upper limit, mechanical strength, etc. can be made still more favorable.

The content of the ionomer resin in the ionomer resin layer (B) according to the present embodiment is preferably 50% by mass or more, more preferably 60% by mass or more, based on 100% by mass of the entire ionomer resin layer (B). It is more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more. When the content of the ionomer resin in the ionomer resin layer (B) according to the present embodiment is not less than the above lower limit value, the balance of the processability such as processability, interlayer adhesion, transparency, and mechanical strength of the laminate 10 can be obtained. It can be made even better.
The upper limit of the content of the ionomer resin in the ionomer resin layer (B) according to the present embodiment is not particularly limited, and is, for example, 100% by mass or less.

Various additives can be contained in the ionomer resin layer (B) according to the present embodiment as long as the object of the present invention is not impaired. Although various additives are not particularly limited, for example, plasticizers, antioxidants, ultraviolet absorbers, wavelength converting agents, antistatic agents, surfactants, coloring agents, light stabilizers, foaming agents, lubricants, crystal nuclei Agents, crystallization accelerators, crystallization retarders, catalyst deactivators, heat ray absorbents, heat ray reflectors, heat radiating agents, thermoplastic resins other than ionomer resins, thermosetting resins, inorganic fillers, organic fillers, resistance Impact modifiers, slip agents, crosslinkers, crosslinking aids, tackifiers, silane coupling agents, processing aids, mold release agents, hydrolysis inhibitors, heat resistant stabilizers, anti blocking agents, antifogging agents, hard A flame retardant, a flame retardant auxiliary agent, a light diffusing agent, an antibacterial agent, a mildew-proof agent, a dispersing agent, other resin etc. can be mentioned. The various additives may be used singly or in combination of two or more.

<Adhesive resin layer (C)>
The adhesive resin layer (C) according to the present embodiment comprises at least one ethylene / polar monomer copolymer (C1) selected from ethylene / vinyl ester copolymer and ethylene / unsaturated carboxylic acid ester copolymer And an adhesive resin composition (P) containing a glycidyl group-containing ethylene copolymer (C2) (but excluding ethylene / polar monomer copolymer (C1)).

In the adhesive resin composition (P) according to the present embodiment, the content of the polar monomer in the ethylene / polar monomer copolymer (C1) is the thermoplastic polyurethane resin layer (A) and the ionomer resin layer (B) From the viewpoint of improving the interlayer adhesiveness of the laminate and the flexibility of the resulting laminate 10, the content is preferably 21% by mass or more, more preferably 23% by mass or more, based on the entire resin component in the adhesive resin composition (P). It is more preferably 25% by mass or more, still more preferably 28% by mass or more, and particularly preferably 30% by mass or more.
Further, the upper limit of the content of the polar monomer in the ethylene / polar monomer copolymer (C1) is not particularly limited, but from the viewpoint of making the mechanical properties, heat resistance, handleability and processability of the laminate 10 better. The amount is preferably 55% by mass or less, more preferably 50% by mass or less, still more preferably 45% by mass or less, still more preferably 40% by mass or less, based on the entire resin component in the adhesive resin composition (P). Is 38 mass% or less.
When the polar monomer is vinyl acetate, the content of the polar monomer can be measured, for example, in accordance with JIS K7192: 1999.
When the polar monomer is an unsaturated carboxylic acid ester, the content of the polar monomer is measured, for example, by an infrared absorption spectrum (IR) attributable to the unsaturated carboxylic acid ester. For example, when the unsaturated carboxylic acid ester is ethyl acrylate (EA), it is determined from the absorbance at 860 cm ^-1 attributable to EA. However, the calibration curve is obtained by determining the EA concentration by nuclear magnetic resonance spectrum (NMR) and correlating it with the absorbance at 860 cm ^-1 of IR.
Further, in the present embodiment, the entire resin component in the adhesive resin composition (P) refers to the ethylene / polar monomer copolymer (C1), the glycidyl group-containing ethylene copolymer (C2), ethylene / polyamide described later, and the like. It means the total amount of resin components such as resins contained in the polar monomer copolymer (C3) and other components.
The thermoplastic polyurethane resin layer (the ethylene-polar monomer copolymer (C1) having a polar monomer content equal to or more than the above lower limit value and the glycidyl group-containing ethylene copolymer (C2) in combination Higher adhesion to A) can be achieved.

In the adhesive resin composition (P) according to the present embodiment, the total content of the content of the ethylene / polar monomer copolymer (C1) and the content of the glycidyl group-containing ethylene copolymer (C2) is The total content of the adhesive resin composition (P) is 100% by mass, preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, particularly preferably 90% by mass or more . Adhesive resin layer (C) obtained when the total content of the content of the ethylene / polar monomer copolymer (C1) and the content of the glycidyl group-containing ethylene copolymer (C2) is within the above range It is possible to further improve the balance of adhesion, flexibility, mechanical properties, heat resistance, handleability, processability and the like.
The upper limit of the total content of the content of the ethylene / polar monomer copolymer (C1) and the content of the glycidyl group-containing ethylene copolymer (C2) is not particularly limited, but from the viewpoint of adhesiveness, the adhesiveness When the whole of a resin composition (P) is 100 mass%, it is preferably 100 mass% or less, more preferably 98 mass% or less.

In the adhesive resin composition (P) according to the present embodiment, the content of the ethylene / polar monomer copolymer (C1) is 50%, based on 100% by mass of the entire adhesive resin composition (P). % Or more and 99% by mass or less is preferable, 60% by mass or more and 98% by mass or less is more preferable, and 70% by mass or more and 97% by mass or less is particularly preferable. Adhesiveness, flexibility, mechanical properties, heat resistance, handleability, processability, etc. of the adhesive resin layer (C) obtained when the content of the ethylene / polar monomer copolymer (C1) is within the above range Can be made even better.

In the adhesive resin composition (P) according to the present embodiment, the glycidyl group-containing ethylene copolymer (C2) is 1% by mass or more, based on 100% by mass of the entire adhesive resin composition (P). 50 mass% or less is preferable, 2 mass% or more and 40 mass% or less are more preferable, and 3 mass% or more and 30 mass% or less are especially preferable. Adhesiveness, flexibility, mechanical characteristics, heat resistance, handleability, processability of the adhesive resin layer (C) obtained as the content of the glycidyl group-containing ethylene copolymer (C2) is within the above range Etc. can be further improved.
When content of the whole resin component in adhesive resin composition (P) is 100 mass%, 0.05 mass% or more and 10 mass% or less are preferable, and content of glycidyl group is 0.08 mass% or more and 8 mass% or less Is more preferably 0.1% by mass to 5% by mass, and still more preferably 0.1% by mass to 1% by mass.

In the laminate 10 according to the present embodiment, the mass of the content of the ethylene / polar monomer copolymer (C1) relative to the content of the glycidyl group-containing ethylene copolymer (C2) in the adhesive resin composition (P) The ratio is preferably 1 or more and 50 or less, more preferably 1 or more and 30 or less, and still more preferably 5 or more and 25 or less. As a result, the balance between the interlayer adhesion and the flexibility, the mechanical properties, the heat resistance, the handleability, the processability and the like of the laminate 10 can be further improved.

In the adhesive resin composition (P) according to the present embodiment, the flexural rigidity measured under conditions of a temperature of 23 ° C. according to JIS K 7106: 1995 is preferably 40 MPa or less, and 30 MPa or less Is more preferable, and 20 MPa or less is particularly preferable. When the flexural rigidity satisfies the above range, the balance of the adhesiveness, the flexibility, the handleability, the processability and the like of the laminate 10 can be further improved. In order to achieve such a flexural rigidity, the composition of the adhesive resin composition (P) may be appropriately adjusted.
The lower limit value of the flexural rigidity is not particularly limited, but is preferably 1 MPa or more, more preferably 2 MPa or more from the viewpoint of improving heat resistance and mechanical properties.

In adhesive resin composition (P) which concerns on this embodiment, content of the carboxylic acid modified resin in adhesive resin composition (P) made the whole of adhesive resin composition (P) 100 mass%. The amount is preferably 4% by mass or less, more preferably 1% by mass or less, still more preferably 0.5% by mass or less, still more preferably 0.1% by mass or less, and particularly preferably 0.05% by mass or less. The carboxyl group in the carboxylic acid modified resin may react with the glycidyl group in the glycidyl group-containing ethylene copolymer (C2) to form a gel. Therefore, when the content of the carboxylic acid-modified resin in the adhesive resin composition (P) is less than or equal to the above upper limit, the adhesive resin composition (P) may gelate during processing or preparation, or a resin layer obtained Generation of aggregates can be suppressed.
Here, as carboxylic acid modified resin, modified polyolefin resin etc. which grafted or copolymerized unsaturated carboxylic acid or its derivative are mentioned to polyolefin resin, such as polyethylene resin and polypropylene resin, for example are mentioned.

Hereinafter, each component which comprises adhesive resin composition (P) is demonstrated.

(Ethylene / polar monomer copolymer (C1))
The ethylene-polar monomer copolymer (C1) according to the present embodiment contains at least one selected from an ethylene-vinyl ester copolymer and an ethylene-unsaturated carboxylic acid ester copolymer. In the present embodiment, the polar monomer means a monomer having a functional group. Here, the glycidyl group-containing ethylene copolymer (C2) is not included in the ethylene / polar monomer copolymer (C1) according to the present embodiment.

Examples of the ethylene / vinyl ester copolymer according to the present embodiment include ethylene / vinyl acetate copolymer, ethylene / vinyl propionate copolymer, ethylene / vinyl butyrate copolymer, ethylene / vinyl stearate copolymer One or two or more selected from etc. can be used.

The ethylene / unsaturated carboxylic acid ester copolymer according to the present embodiment is a polymer obtained by copolymerizing ethylene and at least one unsaturated carboxylic acid ester.
Specifically, a copolymer comprising ethylene and an alkyl ester of unsaturated carboxylic acid can be exemplified.

Examples of the unsaturated carboxylic acid in the unsaturated carboxylic acid ester include acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and the like.
Examples of the alkyl moiety in the alkyl ester of unsaturated carboxylic acid include those having 1 to 12 carbon atoms, and more specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl And alkyl groups such as 2-ethylhexyl and isooctyl. In the present embodiment, the carbon number of the alkyl moiety of the alkyl ester is preferably 1 to 8.

As unsaturated carboxylic acid esters, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, isobutyl (meth) acrylate, (meth) acrylate It is preferable to include one or more selected from (meth) acrylic acid esters such as n-butyl, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and the like. These unsaturated carboxylic acid esters may be used alone or in combination of two or more. Among these, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, isobutyl (meth) acrylate, n-butyl (meth) acrylate and the like It is more preferable to include one or two or more selected from

In the present embodiment, a preferred ethylene / unsaturated carboxylic acid ester copolymer is an ethylene / (meth) acrylic acid ester copolymer. Among them, copolymers composed of one kind of compound as (meth) acrylic acid ester are preferable. As such a copolymer, ethylene (meth) acrylate methyl copolymer, ethylene (ethyl) (meth) acrylate copolymer, ethylene (meth) acrylate copolymer, ethylene (meth) N-propyl acrylate copolymer, isobutyl copolymer of ethylene (meth) acrylate, n-butyl copolymer of ethylene (meth) acrylate, isooctyl copolymer of ethylene (meth) acrylate, ethylene ( And (meth) acrylic acid 2-ethylhexyl copolymer and the like.

Ethylene / polar monomer copolymer (C1) is ethylene / vinyl acetate copolymer, ethylene / methyl (meth) acrylate copolymer, ethylene / ethyl (meth) acrylate copolymer, ethylene / (meth) acrylic 1 type selected from isopropyl acid isopropyl copolymer, ethylene / (meth) acrylic acid n-propyl copolymer, ethylene / (meth) acrylic acid isobutyl copolymer, ethylene / (meth) acrylic acid n-butyl copolymer It is preferable to contain 2 or more types, and it is more preferable to contain an ethylene-vinyl acetate copolymer.
In the present embodiment, the ethylene / polar monomer copolymer (C1) may be used alone or in combination of two or more.

In the embodiment, from the viewpoint of further improving the processing stability, the melt flow rate of the ethylene / polar monomer copolymer (C1) measured under the conditions of 190 ° C. and 2160 g load in accordance with JIS K 7210: 1999 The MFR) is preferably 0.1 g / 10 minutes or more and 150 g / 10 minutes or less, more preferably 0.2 g / 10 minutes or more and 100 g / 10 minutes or less, and more preferably 0.5 g / 10 minutes or more and 50 g / minute. More preferably, it is 10 minutes or less.
The MFR of the ethylene-polar monomer copolymer (C1) may be adjusted by blending a plurality of ethylene-polar monomer copolymers (C1) having different MFRs.

The method for producing the ethylene / polar monomer copolymer (C1) according to the present embodiment is not particularly limited, and can be produced by a known method. For example, it can be obtained by radical copolymerization of each polymerization component under high temperature and high pressure. Moreover, you may use what is marketed for ethylene and a polar monomer copolymer (C1).

(Glycidyl group-containing ethylene copolymer (C2))
The glycidyl group-containing ethylene-based copolymer (C2) according to the present embodiment is a polymer obtained by copolymerizing ethylene and at least one glycidyl group-containing monomer, and as the glycidyl group-containing monomer, for example, (meth) acrylic Acid glycidyl is mentioned. Examples of the glycidyl group-containing ethylene copolymer (C2) include ethylene / (meth) acrylic acid glycidyl copolymer, ethylene / (meth) acrylic acid glycidyl / vinyl acetate copolymer, and ethylene / (meth) acrylic acid 1 type, or 2 or more types selected from acid glycidyl (meth) acrylic acid ester copolymer etc. are mentioned.

The content ratio of the structural unit derived from glycidyl (meth) acrylate in the glycidyl group-containing ethylene copolymer (C2) is preferably 2% by mass to 30% by mass, more preferably 3% by mass to 25% by mass. It is below.
When the content ratio of the structural unit derived from (glyc) (meth) acrylate is within the above range, the balance of the interlayer adhesion, the flexibility, the handleability, the processability, etc. of the laminate 10 is further improved. Can.
In addition, "(meth) acrylic acid glycidyl" represents at least one or both of glycidyl methacrylate and glycidyl acrylate.

The "ethylene-based copolymer" in the glycidyl-group-containing ethylene-based copolymer (C2) means that a constituent unit derived from ethylene is a main component. Furthermore, "the main component" here means that the content of "the structural unit derived from ethylene" is the highest among all the structural units. For example, in the case of a copolymer consisting of structural units derived from ethylene, glycidyl (meth) acrylate and vinyl acetate, the ratio of structural units derived from ethylene is a structural unit derived from glycidyl (meth) acrylate Or larger than a structural unit derived from vinyl acetate.
The proportion of the “constituent unit derived from ethylene” in the glycidyl group-containing ethylene copolymer (C2) is preferably 65% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more. The upper limit of the proportion of the “constituent unit derived from ethylene” in the glycidyl group-containing ethylene copolymer (C2) is not particularly limited, but is, for example, 98 mass% or less, preferably 97 mass% or less, more preferably 96 It is less than mass%. At this time, the ethylene-based copolymer may further include other monomer units (eg, vinyl acetate, (meth) acrylic acid ester, etc.) other than ethylene and glycidyl (meth) acrylate.

Specifically, in addition to the copolymer containing a structural unit derived from ethylene and a structural unit derived from glycidyl (meth) acrylate, in addition to these two structural units, a structure further derived from vinyl acetate The copolymer which contains a unit and at least one of the structural unit derived from (meth) acrylic acid ester is mentioned.
The total content of structural units derived from vinyl acetate and structural units derived from (meth) acrylic acid ester is preferably 30% by mass or less, and more preferably 20% by mass or less.

The lower limit of the total of the content ratio of the constituent unit derived from vinyl acetate and the constituent unit derived from (meth) acrylic acid ester is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5 % By mass or more, more preferably 1% by mass or more is desirable. Furthermore, the total content of structural units derived from vinyl acetate and structural units derived from (meth) acrylate is preferably in the range of 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, In particular, the range of 1 to 20% by mass is preferable.

The glycidyl group-containing ethylene-based copolymer (C2) may be used alone or in combination of two or more kinds of copolymers different in copolymerization ratio etc. or two or more kinds of copolymers different in monomer type. it can.

It is preferable that at least a part of the glycidyl group-containing ethylene copolymer (C2) is modified by a silane coupling agent. Thereby, the interlayer adhesion between the thermoplastic polyurethane resin layer (A) and the ionomer resin layer (B) can be further improved.

Here, in the adhesive resin composition (P) according to the present embodiment, the silane coupling agent in the glycidyl group-containing ethylene copolymer (C2) is a silane coupling agent having a polymerizable group, an amino group It is preferable to include one or more selected from the group consisting of a silane coupling agent having an epoxy group and a silane coupling agent having an epoxy group.
Here, modification of the silane coupling agent to the glycidyl group-containing ethylene copolymer (C2) is carried out, for example, by using a glycidyl group-containing ethylene copolymer (C2) and a silane coupling agent having an amino group or an epoxy group. And a reaction (for example, 100 ° C. to 200 ° C.) under heating (modification method 1) or a silane having a polymerizable group in a glycidyl group-containing ethylene copolymer (C2) using a polymerization initiator There is a method of graft polymerization of a coupling agent (modification method 2) and the like.
In Modification Method 1, the amino group or epoxy group in the silane coupling agent and the glycidyl group in the glycidyl group-containing ethylene copolymer (C2) react with each other to form a glycidyl group-containing ethylene copolymer ( A silane coupling agent is introduced into the side chain of C2).
In the modification method 2, for example, a glycidyl group-containing ethylene-based copolymer (C2), a silane coupling agent having a polymerizable group, and a radical polymerization initiator, using an extruder, a kneader, a Banbury mixer, etc. It can manufacture by melt-kneading at the temperature more than melting | fusing point of a glycidyl group containing ethylene-based copolymer (C2), and the decomposition temperature of a radical polymerization initiator. These reactions can also be carried out in solution.

As a polymerization initiator, although what is normally used can be used, an organic peroxide is preferable.
As the organic peroxide, known organic peroxides usable as a polymerization initiator can be used. Specifically, diacyl peroxide compounds, alkyl peroxy ester compounds, peroxy dicarbonate compounds, peroxy carbonates Examples thereof include compounds, peroxyketal compounds, dialkyl peroxide compounds, hydroperoxide compounds, ketone peroxide compounds and the like.
Among them, dialkyl peroxide compounds are preferable, and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,3-di (2-t-butylperoxyisopropyl) benzene, di-t- More preferred is butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3.

As a silane coupling agent having a polymerizable group, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, Examples thereof include 3-methacryloxypropyltriethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-acryloxypropyltriethoxysilane and the like.
As a silane coupling agent having an amino group, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (2) Aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N- Phenyl-3-aminopropyltrimethoxysilane, hydrochloride of N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane and the like can be mentioned.
As a silane coupling agent having an epoxy group, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidone And xylpropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane and the like.

In this embodiment, the melt flow rate of the glycidyl group-containing ethylene copolymer (C2) measured under the conditions of 190 ° C. and 2160 g load according to JIS K 7210: 199 from the viewpoint of further improving processing stability (MFR) is preferably 0.1 g / 10 minutes to 50 g / 10 minutes, more preferably 0.5 g / 10 minutes to 30 g / 10 minutes, and 1 g / 10 minutes to 20 g / 10 minutes. More preferably, it is less than a minute.

The polymerization initiator used for modification is usually contained in an amount of 0.1 to 5 parts by mass, preferably 0.5 to 3 parts by mass, per 100 parts by mass of the glycidyl group-containing ethylene copolymer (C2). it can.
The silane coupling agent can be contained in an amount of usually 5 parts by mass or less, preferably 0.02 to 3 parts by mass, per 100 parts by mass of the glycidyl group-containing ethylene copolymer (C2). When the silane coupling agent is contained in the above range, the adhesion to the thermoplastic polyurethane resin layer can be further improved.

(Ethylene / polar monomer copolymer (C3))
The adhesive resin composition (P) according to the present embodiment preferably further includes an ethylene / polar monomer copolymer (C3) modified by a silane coupling agent. Thereby, the interlayer adhesion between the thermoplastic polyurethane resin layer (A) and the ionomer resin layer (B) can be further improved. Here, the ethylene / polar monomer copolymer (C1) and the glycidyl group-containing ethylene copolymer (C2) are not included in the ethylene / polar monomer copolymer (C3) according to the present embodiment.

Examples of the ethylene-polar monomer copolymer in the ethylene-polar monomer copolymer (C3) according to this embodiment include an ethylene-vinyl ester copolymer, an ethylene-unsaturated carboxylic acid ester copolymer, and the like. .

The ethylene / vinyl ester copolymer is selected, for example, from ethylene / vinyl acetate copolymer, ethylene / vinyl propionate copolymer, ethylene / vinyl butyrate copolymer, ethylene / vinyl stearate copolymer, etc. One kind or two or more kinds can be used.

The ethylene / polar monomer copolymer in the ethylene / polar monomer copolymer (C3) is ethylene / vinyl acetate copolymer, ethylene / methyl (meth) acrylate copolymer, ethylene / ethyl (meth) acrylate copolymer Combined, ethylene (isopropyl) (meth) acrylate copolymer, ethylene (meth) acrylate n-propyl copolymer, ethylene (meth) acrylate isobutyl copolymer, ethylene (meth) acrylate n-butyl It is preferable to include one or more selected from copolymers, and it is more preferable to include an ethylene-vinyl acetate copolymer.
In the present embodiment, the ethylene / polar monomer copolymer (C3) may be used alone or in combination of two or more.

The content of the polar monomer in the ethylene-polar monomer copolymer in the ethylene-polar monomer copolymer (C3) is preferably 5% by mass to 50% by mass, and more preferably 8% by mass to 45% by mass Or less, particularly preferably 8% by mass or more and 30% by mass or less.
When the polar monomer is vinyl acetate, the content of the polar monomer can be measured, for example, in accordance with JIS K7192: 1999. When the polar monomer is an unsaturated carboxylic acid ester, the content of the polar monomer is measured, for example, by an infrared absorption spectrum (IR) attributable to the unsaturated carboxylic acid ester. For example, when the unsaturated carboxylic acid ester is ethyl acrylate (EA), it is determined from the absorbance at 860 cm ^-1 attributable to EA. However, the calibration curve is obtained by determining the EA concentration by nuclear magnetic resonance spectrum (NMR) and correlating it with the absorbance at 860 cm ^-1 of IR.

In the embodiment, from the viewpoint of further improving the processing stability, the melt flow rate of the ethylene / polar monomer copolymer (C3) (measured under the conditions of 190 ° C., 2160 g load) according to JIS K 7210: 1999 The MFR) is preferably 0.1 g / 10 minutes to 300 g / 10 minutes, more preferably 0.2 g / 10 minutes to 200 g / 10 minutes, and more preferably 0.5 g / 10 minutes to 180 g / minute. More preferably, it is 10 minutes or less.
The MFR of the ethylene-polar monomer copolymer (C3) may be adjusted by blending a plurality of ethylene-polar monomer copolymers (C3) having different MFRs.

The method for producing the ethylene-polar monomer copolymer in the ethylene-polar monomer copolymer (C3) according to the present embodiment is not particularly limited, and can be produced by a known method. For example, it can be obtained by radical copolymerization of each polymerization component under high temperature and high pressure. In addition, as the ethylene / polar monomer copolymer in the ethylene / polar monomer copolymer (C3), commercially available ones may be used.

At least a part of the ethylene / polar monomer copolymer (C3) is modified by a silane coupling agent. Thereby, the interlayer adhesion between the thermoplastic polyurethane resin layer (A) and the ionomer resin layer (B) can be further improved.

Here, the above-mentioned silane coupling agent in the ethylene / polar monomer copolymer (C3) according to the present embodiment is a silane coupling agent having a polymerizable group, a silane coupling agent having an amino group, and a silane cup having an epoxy group. It is preferable to include one or more selected from the group consisting of ring agents.
Here, the modification of the silane coupling agent to the ethylene / polar monomer copolymer (C3) is, for example, the same method as the modification of the silane coupling agent to the glycidyl group-containing ethylene copolymer (C2) described above Can be mentioned.
In addition, modification of the silane coupling agent to the ethylene / polar monomer copolymer (C3) and modification of the silane coupling agent to the glycidyl group-containing ethylene copolymer (C2) may be performed simultaneously.

Here, when simultaneously modifying the silane coupling agent to the ethylene / polar monomer copolymer (C3) and modifying the silane coupling agent to the glycidyl group-containing ethylene copolymer (C2), The polymerization initiator used is, for example, 0.1 to 5 parts by mass, preferably 0.2 based on a total of 100 parts by mass of the glycidyl group-containing ethylene copolymer (C2) and the ethylene / polar monomer copolymer (C3). It can be contained in an amount of up to 3 parts by mass.
The silane coupling agent is, for example, 5 parts by mass or less, preferably 0.02 to 3 parts by mass, based on 100 parts by mass of the glycidyl group-containing ethylene copolymer (C2) and the ethylene / polar monomer copolymer (C3) in total. It can be contained in part quantities. When the silane coupling agent is contained in the above range, the interlayer adhesion between the thermoplastic polyurethane resin layer (A) and the ionomer resin layer (B) can be further improved.
The content of the silane coupling agent is preferably 0.01% by mass or more and 2% by mass or less, and 0.05% by mass or more, based on 100% by mass of the entire resin component in the adhesive resin composition (P). It is more preferably at most 0% by mass. Here, the above content of the silane coupling agent also includes a silane coupling agent grafted to the glycidyl group-containing ethylene copolymer (C2) and the ethylene / polar monomer copolymer (C3).

(Other ingredients)
In the adhesive resin composition (P) according to the present embodiment, an ethylene / polar monomer copolymer (C1), a glycidyl group-containing ethylene copolymer (C2), and a range in which the effects of the present invention are not impaired Resins and additives other than the ethylene / polar monomer copolymer (C3) may be contained.
The other resin is not particularly limited, and polyethylene, polypropylene, polybutene and the like can be mentioned. The additive is not particularly limited. For example, plasticizers, antioxidants, UV absorbers, antistatic agents, surfactants, colorants, light stabilizers, foaming agents, lubricants, crystal nucleating agents, and crystallization promotion Agents, crystallization retarders, catalyst deactivators, inorganic fillers, organic fillers, impact modifiers, slip agents, crosslinking agents, crosslinking aids, tackifiers, silane coupling agents, processing aids, release agents Mold inhibitors, hydrolysis inhibitors, heat resistant stabilizers, anti blocking agents, antifogging agents, flame retardants, flame retardant aids, heat radiating agents, light diffusing agents, antibacterial agents, mildew proofing agents, dispersing agents, etc. . The other components may be used alone or in combination of two or more.

(Preparation method of adhesive resin composition (P))
The method for preparing the adhesive resin composition (P) is not particularly limited. For example, an ethylene / polar monomer copolymer (C1), a glycidyl group-containing ethylene copolymer (C2), and optionally ethylene may be used. · A method of preparing by dry blending and mixing a polar monomer copolymer (C3), another resin, and an additive, an ethylene · polar monomer copolymer (C1), and a glycidyl group-containing ethylene system The method of preparing by melt-kneading a copolymer (C2), an ethylene-polar monomer copolymer (C3), other resin, and an additive according to need by an extruder, etc. are applied be able to.

2. Method for Producing Laminate The method for producing the laminate 10 according to the present embodiment is not particularly limited, and a molding method generally used for thermoplastic resins can be applied. For example, it can be carried out by a known method using a T-die extruder, an inflation molding machine or the like.
For example, the adhesive resin composition (P) for forming the adhesive resin layer (C) is supplied from the hopper of a T-die extruder and adhered onto the thermoplastic polyurethane resin layer (A) from the tip of the T die. Resin layer (C) is extruded into a film, and then a resin composition for forming the ionomer resin layer (B) is supplied from the hopper of the T-die extruder and adhesive resin is obtained from the tip of the T-die It can be obtained by extruding the ionomer resin layer (B) on the layer (C) in the form of a film. Alternatively, the adhesive resin layer (C) and the ionomer resin layer (B) may be coextruded into a film by a multilayer T-die extruder, and then the thermoplastic polyurethane resin layer (A) may be extruded to the film.

Moreover, the manufacturing method of the multilayer film generally used can be applied in the manufacturing method of the laminated body 10 which concerns on this embodiment. For example, it can be carried out by a known method using a multilayer T-die extruder or a multilayer inflation molding machine or the like.
For example, a resin composition for forming a thermoplastic polyurethane resin layer (A), an adhesive resin composition (P) for forming an adhesive resin layer (C), and an ionomer resin layer (B) are formed. The resin composition to be used can be obtained by co-extrusion into a sheet form from the T-die tip by supplying from the main extruder of the multilayer T-die extruder and the hopper of the secondary extruder.
When forming a pressure-sensitive adhesive layer (D), a method of extruding a pressure-sensitive adhesive on any one of the obtained multilayer films with a T-die extruder, or co-extrusion of all the components to form a sheet You can also.

Although the embodiments of the present invention have been described above with reference to the drawings, these are merely examples of the present invention, and various configurations other than the above can also be adopted.

EXAMPLES Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples.

The detail of the component used for preparation of a laminated body is as follows.

<Thermoplastic polyurethane resin>
TPU 1: Polycarbonate-based thermoplastic polyurethane resin (manufactured by Nippon Milactolan Co., Ltd., XN 2004 S, hardness 96 A, pellet was used after drying at 90 ° C. for 24 hours)
<Ionomer of ethylene / unsaturated carboxylic acid copolymer>
EMAc 1: Ionomer of ethylene / methacrylic acid copolymer (ethylene content 85% by mass, methacrylic acid content: 15% by mass, 59% zinc neutralization, melting point: 89 ° C.)
EMAc2: Ionomer of ethylene / methacrylic acid copolymer (ethylene content 90% by mass, methacrylic acid content: 10% by mass, 63% zinc neutralization, melting point: 95 ° C.)

<Preparation of Adhesive Resin Composition (P1)>
Ethylene, glycidyl methacrylate, vinyl acetate copolymer (EGMAVA, manufactured by Sumitomo Chemical Co., Ltd., Bondfast 7B, ethylene content: 83% by mass, glycidyl methacrylate content: 12% by mass, vinyl acetate content: 5% %, MFR (190 ° C., 2160 g load): 7 g / 10 minutes: 49.1 parts by mass, ethylene / vinyl acetate copolymer (vinyl acetate content: 15% by mass): 49.1 parts by mass, 3-methacrylic acid Roxypropyl trimethoxysilane (Shin-Etsu Chemical Co., Ltd., trade name "KBM 503"): 1.5 parts by mass and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (alkema Yoshitomi ( Manufactured by Co., Ltd., trade name "RUPEROX 101"): 0.3 parts by mass are mixed beforehand, and EGMAVA and Glycidyl group-containing ethylene copolymer and ethylene / polar monomer modified with a silane coupling agent by graft-modifying a silane coupling agent, 3-methacryloxypropyltrimethoxysilane, with a styrene / vinyl acetate copolymer A mixture of copolymers (P0) was obtained.
Then, 90 parts by mass of ethylene / vinyl acetate copolymer (vinyl acetate content: 33% by mass) and 10 parts by mass of mixture (P0) are put into an extruder, and the adhesive resin composition is prepared by melt kneading under the following conditions. A substance (P1) was prepared.
Extruder: 40 mm profile extruder (L / D = 26 mm, manufactured by Nakatani Corporation)
Kneading conditions: Temperature: 180 ° C., rotational speed: 60 min ^-1

Example 1
Using TPU1 as the outer layer 1, adhesive resin composition (P1) as the intermediate layer, and EMAc2 as the outer layer 2, using a multilayer T-die molding machine, the thickness ratio is as follows: outer layer 1 / intermediate layer / outer layer 2 = 80 μm / 20 μm / 50 μm to make a laminate having a total thickness of 150 μm, and the following evaluations were performed. The obtained results are shown in Table 1.
Here, the molding temperature of the outer layer 1 was 200 ° C., the molding temperature of the intermediate layer was 230 ° C., and the molding temperature of the outer layer 2 was 250 ° C.

Example 2
Using TPU1 as the outer layer 1, adhesive resin composition (P1) as the intermediate layer, and EMAc1 as the outer layer 2, using a multilayer T-die molding machine, the thickness ratio is as follows: outer layer 1 / intermediate layer / outer layer 2 = 80 μm / 20 μm / 50 μm to make a laminate having a total thickness of 150 μm, and the following evaluations were performed. The obtained results are shown in Table 1.
Here, the molding temperature of the outer layer 1 was 200 ° C., the molding temperature of the intermediate layer was 230 ° C., and the molding temperature of the outer layer 2 was 250 ° C.

Comparative Example 1
Using TPU1 as the outer layer 1, EMAc2 as the intermediate layer, and EMAc2 as the outer layer 2, using a multilayer T-die molding machine, the thickness ratio is made 1 / intermediate layer / outer layer 2 = 80 μm / 20 μm / 50 μm and the total thickness is 150 μm The following laminates were produced and evaluated as follows. The obtained results are shown in Table 1.
Here, the molding temperature of the outer layer 1 was 200 ° C., the molding temperature of the intermediate layer was 250 ° C., and the molding temperature of the outer layer 2 was 250 ° C.

Comparative Example 2
Using TPU1 as the outer layer 1, EMAc1 as the intermediate layer, EMAc1 as the outer layer 2, and using a T-die molding machine, the thickness ratio is made 1 / intermediate layer / outer layer 2 = 80 μm / 20 μm / 50 μm, and the total thickness is 150 μm Laminates were produced and evaluated as follows. The obtained results are shown in Table 1.
Here, the molding temperature of the outer layer 1 was 200 ° C., the molding temperature of the intermediate layer was 250 ° C., and the molding temperature of the outer layer 2 was 250 ° C.

Comparative Example 3
Using a mixture of TPU1 as the outer layer 1, EMAc2 / TPU1 = 50/50 (mass ratio) as the intermediate layer, and EMAc1 as the outer layer 2, using a T-die molding machine, the thickness ratio is as follows: outer layer 1 / intermediate layer / outer layer 2 A laminate having a total thickness of 150 μm was manufactured to be 80 μm / 20 μm / 50 μm, and the following evaluations were performed. The obtained results are shown in Table 1.
Here, the molding temperature of the outer layer 1 was 200 ° C., the molding temperature of the intermediate layer was 260 ° C., and the molding temperature of the outer layer 2 was 250 ° C.

Comparative Example 4
TPU1 is used as the outer layer 1, TPU1 as the intermediate layer, TPU1 as the outer layer 2, and using a T-die molding machine, the thickness ratio is made outer layer 1 / intermediate layer / outer layer 2 = 80 μm / 20 μm / 50 μm, and the total thickness is 150 μm Laminates were produced and evaluated as follows. The obtained results are shown in Table 1.
Here, the molding temperature of the outer layer 1 was 200 ° C., the molding temperature of the intermediate layer was 200 ° C., and the molding temperature of the outer layer 2 was 200 ° C.

<Evaluation>
(1) Stress at break and elongation between marks Measured using a tensile tester (Autograph precision universal tester AG-X, manufactured by Shimadzu Corporation) in accordance with JIS K 6781: 1994. The measurement was performed by cutting the laminate into a size of No. 1 dumbbell as a test piece, and pulling the test piece under the conditions of a distance between chucks of 90 mm and a tensile speed of 50 mm / min. In addition, the said tensile test was done in 23 degreeC and the environment of 50% of a relative humidity. Here, as the stress at break and the elongation between marks of the laminate, an average value of the values in the MD direction and the values in the TD direction was adopted.

(2) Transparency Test pieces of 50 mm × 50 mm were cut out from the laminate, and in accordance with JIS K7136: 2000, using a haze / transmittance meter HM-150 manufactured by Murakami Color Research Laboratory, Inc., Haze and total light transmittance were measured respectively.

(3) Interlayer adhesive strength A test piece of 15 mm width was cut out from the laminate, and the distance between chucks: 90 mm, tensile speed using a tensile tester Autograph AG-X manufactured by Shimadzu Corporation in accordance with JIS Z1707: 1997. : The interlayer adhesive strength of the thermoplastic polyurethane resin layer (A) and the ionomer resin layer (B) in the test piece was measured under the condition of 500 mm / min.

(4) Contamination resistance The surface of the outer layer 2 of the laminate was soiled with an oil-based pen (Magic Ink No. 500 manufactured by Terasai Chemical Industry Co., Ltd.), and after 4 hours, the soil was wiped off with ethanol. Subsequently, the marks of the oil-based pen were visually observed, and the stain resistance of the laminate was evaluated based on the following criteria.
:: No mark of oil-based pen observed or faintly observed ×: Mark of oil-based pen clearly observed

The laminates of Examples 1 and 2 were excellent in the performance balance of flexibility, mechanical strength, transparency, interlayer adhesion, and stain resistance. On the other hand, the laminates of Comparative Examples 1 to 4 were inferior in the performance balance of flexibility, mechanical strength, transparency, interlayer adhesion, and stain resistance.

This application claims priority based on Japanese Patent Application No. 2017-240621, filed Dec. 15, 2017, the entire disclosure of which is incorporated herein.

Claims

Thermoplastic polyurethane resin layer (A), ionomer resin layer (B), adhesive resin layer (C) provided between the thermoplastic polyurethane resin layer (A) and the ionomer resin layer (B) And a laminate comprising
The adhesive resin layer (C) comprises at least one ethylene / polar monomer copolymer (C1) selected from ethylene / vinyl ester copolymer and ethylene / unsaturated carboxylic acid ester copolymer, and glycidyl group-containing A laminate comprising an adhesive resin composition comprising an ethylene-based copolymer (C2) (but excluding the ethylene / polar monomer copolymer (C1)).
In the laminate according to claim 1,
The adhesive resin composition comprises an ethylene-polar monomer copolymer (C3) modified with a silane coupling agent (with the proviso that the ethylene-polar monomer copolymer (C1) and the glycidyl group-containing ethylene copolymer (C3) A laminate further including C2).
In the laminate according to claim 2,
A laminate comprising the ethylene / polar monomer copolymer (C3) is an ethylene / vinyl acetate copolymer.
In the laminate according to claim 2 or 3,
The silane coupling agent in the modification of the ethylene / polar monomer copolymer (C3) comprises a silane coupling agent having a polymerizable group, a silane coupling agent having an amino group, and a silane coupling agent having an epoxy group. A laminate comprising one or more selected from the group.
The laminate according to any one of claims 1 to 4.
The laminated body by which at least one part of the said glycidyl group containing ethylene-based copolymer (C2) is denatured by the silane coupling agent.
In the laminate according to claim 5,
The silane coupling agent in the modification of the glycidyl group-containing ethylene copolymer (C2) is a silane coupling agent having a polymerizable group, a silane coupling agent having an amino group, and a silane coupling agent having an epoxy group. A laminate comprising one or more selected from the group consisting of
The laminate according to any one of claims 1 to 6,
The laminated body in which the said ionomer resin layer (B) contains the ionomer of an ethylene and unsaturated carboxylic acid-type copolymer.
In the laminate according to any one of claims 1 to 7,
A laminate, wherein the mass ratio of the content of the ethylene / polar monomer copolymer (C1) to the content of the glycidyl group-containing ethylene copolymer (C2) in the adhesive resin composition is 1 or more and 30 or less .
The laminate according to any one of claims 1 to 8.
The glycidyl group-containing ethylene copolymer (C2) is ethylene / (meth) acrylate glycidyl copolymer, ethylene / (meth) acrylate glycidyl / vinyl acetate copolymer, and ethylene / (meth) acrylate glycidyl · The laminated body containing 1 type, or 2 or more types selected from the group which consists of a (meth) acrylic acid ester copolymer.
In the laminate according to any one of claims 1 to 9,
The laminated body in which the said ethylene and polar monomer copolymer (C1) contains an ethylene and vinyl acetate copolymer.
The laminate according to any one of claims 1 to 10.
A laminate having a stress at break of 20 MPa or more measured in accordance with JIS K 6781: 1994.
The laminate according to any one of claims 1 to 11.
A laminate having an elongation between marked lines of 100% or more measured in accordance with JIS K6781: 1994.
The laminate according to any one of claims 1 to 12.
Laminated body whose Haze measured based on JISK7136: 2000 is 5% or less.
The laminate according to any one of claims 1 to 13.
A laminate having a total light transmittance of 80% or more measured in accordance with JIS K7136: 2000.
In the laminate according to any one of claims 1 to 14,
The laminated body whose interlayer adhesive strength of the said thermoplastic polyurethane resin layer (A) and the said ionomer resin layer (B) measured based on JISZ1707: 1997 is 1.0 N / 15 mm or more.
In the laminate according to any one of claims 1 to 15,
The laminated body further equipped with an adhesive layer (D) in any one outermost layer.
In the laminate according to claim 16,
The pressure-sensitive adhesive layer (D) is composed of at least one pressure-sensitive adhesive selected from urethane pressure-sensitive adhesives, rubber pressure-sensitive adhesives, silicone pressure-sensitive adhesives, styrene pressure-sensitive adhesives, olefin pressure-sensitive adhesives and acrylic pressure-sensitive adhesives Stacks.
The laminate according to any one of claims 1 to 17.
A laminate selected from the group consisting of a protective film, a pressure resistant hose, a fuel tube, a multilayer tube, a film for clothing, a film for treating body fluid, a medical tape, a waterproof sheet for building materials, an antifouling tape, a repair tape and a masking tape.
The laminate according to any one of claims 1 to 17.
A laminate that is a paint protection film.
The laminate according to any one of claims 1 to 19,
The laminated body used so that the said ionomer resin layer (B) surface may become an air | atmosphere side.