CN108463501B - Adhesive resin composition, laminate, and method for producing laminate - Google Patents
Adhesive resin composition, laminate, and method for producing laminate Download PDFInfo
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- CN108463501B CN108463501B CN201780005693.5A CN201780005693A CN108463501B CN 108463501 B CN108463501 B CN 108463501B CN 201780005693 A CN201780005693 A CN 201780005693A CN 108463501 B CN108463501 B CN 108463501B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
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Abstract
The adhesive resin composition (P) of the present invention is used for forming a resin layer in contact with a thermoplastic polyurethane resin layer, and comprises at least one ethylene/polar monomer copolymer (a) selected from an ethylene/vinyl ester copolymer and an ethylene/unsaturated carboxylic acid ester copolymer, and a glycidyl group-containing ethylene copolymer (B) (wherein the ethylene/polar monomer copolymer (a) is not included). In the adhesive resin composition (P) of the present invention, the content of the polar monomer in the ethylene/polar monomer copolymer (a) is 21 mass% or more with respect to the total resin components in the adhesive resin composition (P).
Description
Technical Field
The invention relates to an adhesive resin composition, a laminate, and a method for producing a laminate.
Background
Thermoplastic polyurethane resins have both soft elasticity like rubber and toughness like hard plastics, and are therefore used in a wide range of fields and applications as typical thermoplastic elastomers.
By laminating a thermoplastic polyurethane resin layer on another resin layer, for example, a polyurethane-based multilayer film can be produced in which the adhesiveness, the handling property, and the like, which are weak points of the thermoplastic polyurethane resin, are improved while the elasticity and the toughness of the thermoplastic polyurethane resin are maintained.
As a technique related to a polyurethane multilayer film, for example, a technique described in patent document 1 can be cited.
Patent document 1 describes a polyurethane-based multilayer film obtained by laminating a thermoplastic polyurethane resin layer (a), an ethylene-vinyl acetate copolymer layer (B) having a vinyl acetate content of 7 to 35 wt%, a polyethylene-based resin layer, or a polypropylene-based resin layer (C) in this order. Here, in patent document 1, the resin layer (C) is finally peeled 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).
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 8-230119
Disclosure of Invention
Problems to be solved by the invention
The technical level required for the use of polyurethane-based multilayer films as multilayer films, particularly films made of polyolefin resins, is increasing. The present inventors have found the following problems with respect to polyurethane-based multilayer films.
According to the research of the inventor of the present application, it is confirmed that: a polyurethane-based multilayer film obtained by providing a resin layer composed of an ethylene/polar monomer copolymer on a thermoplastic polyurethane resin layer has low interlayer adhesiveness and poor workability.
Further, according to the studies of the inventors of the present application, it was confirmed that: when the content of the polar monomer in the ethylene-polar monomer copolymer is increased in order to improve the interlayer adhesiveness between the thermoplastic polyurethane resin layer and the ethylene-polar monomer copolymer layer, the interlayer adhesiveness is improved to some extent, but it is still not sufficiently satisfactory.
That is, the present inventors have found that the interlayer adhesiveness between the thermoplastic polyurethane resin layer and the ethylene/polar monomer copolymer layer cannot be obtained at a high level only by adjusting the polar monomer content in the ethylene/polar monomer copolymer.
From the above, the present inventors have found that a conventional polyurethane multilayer film has room for improvement from the viewpoint of improving the interlayer adhesiveness between the thermoplastic polyurethane resin layer and the ethylene/polar monomer copolymer layer at a high level.
The present invention has been made in view of the above circumstances, and provides a resin composition capable of achieving high adhesiveness to a thermoplastic polyurethane resin layer.
Means for solving the problems
The present inventors have made extensive studies to achieve the above object. As a result, they have found that a resin composition which can achieve high adhesiveness to a thermoplastic polyurethane resin layer can be obtained by using an ethylene/polar monomer copolymer having a polar monomer content of a specific value or more in combination with a glycidyl group-containing ethylene copolymer, and have completed the present invention.
That is, the present invention provides the following adhesive resin composition, laminate, and method for producing laminate.
[1]
An adhesive resin composition for forming a resin layer in contact with a thermoplastic polyurethane resin layer, the adhesive resin composition comprising:
at least one ethylene/polar monomer copolymer (A) selected from the group consisting of ethylene/vinyl ester copolymers and ethylene/unsaturated carboxylic acid ester copolymers; and
a glycidyl group-containing ethylene copolymer (B) (excluding the above-mentioned ethylene/polar monomer copolymer (A)),
the content of the polar monomer in the ethylene/polar monomer copolymer (a) is 21 mass% or more with respect to the total resin components in the adhesive resin composition.
[2]
The adhesive resin composition according to [1], further comprising an ethylene/polar monomer copolymer (C) modified with a silane coupling agent (excluding the ethylene/polar monomer copolymer (A) and the glycidyl group-containing ethylene copolymer (B)).
[3]
The adhesive resin composition according to the above [2], wherein the ethylene/polar monomer copolymer (C) comprises an ethylene/vinyl acetate copolymer.
[4]
The adhesive resin composition according to the above [2] or [3], wherein the silane coupling agent in the modification of the ethylene-polar monomer copolymer (C) comprises one or more selected from the group consisting of 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.
[5]
The adhesive resin composition according to any one of [1] to [4], wherein at least a part of the glycidyl group-containing ethylene copolymer (B) is modified with a silane coupling agent.
[6]
The adhesive resin composition according to [5], wherein the silane coupling agent in the modification of the glycidyl group-containing ethylene copolymer (B) comprises one or more selected from the group consisting of 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.
[7]
The adhesive resin composition according to any one of [1] to [6], wherein a mass ratio of a content of the ethylene-polar monomer copolymer (A) to a content of the glycidyl group-containing ethylene copolymer (B) in the adhesive resin composition is 1 or more and 30 or less.
[8]
The adhesive resin composition according to any one of [1] to [7], wherein the glycidyl group-containing ethylene copolymer (B) comprises one or more selected from the group consisting of an ethylene glycidyl (meth) acrylate copolymer, an ethylene glycidyl (meth) acrylate-vinyl acetate copolymer, and an ethylene glycidyl (meth) acrylate copolymer.
[9]
The adhesive resin composition according to any one of the above [1] to [8], wherein the ethylene/polar monomer copolymer (A) comprises an ethylene/vinyl acetate copolymer.
[10]
The adhesive resin composition according to any one of the above [1] to [9], wherein the content of the carboxylic acid-modified resin in the adhesive resin composition is 4% by mass or less.
[11]
The adhesive resin composition according to any one of [1] to [10], wherein a flexural modulus of rigidity measured at a temperature of 23 ℃ in accordance with JIS K7106 is 40MPa or less.
[12]
A laminate body, comprising:
a thermoplastic polyurethane resin layer; and
a resin layer provided on at least one surface of the thermoplastic polyurethane resin layer, and composed of the adhesive resin composition according to any one of [1] to [11 ].
[13]
The laminate according to [12], wherein the laminate is selected from the group consisting of a pressure-resistant hose, a fuel pipe, a multilayer pipe, a film for clothing, a film for body fluid treatment, a medical tape, a waterproof sheet for building materials, an antifouling tape, a repair tape and a masking tape.
[14]
A method for producing the laminate according to [12] or [13], the method comprising a step of co-extruding the adhesive resin composition according to any one of [1] to [11] and a resin composition containing at least a thermoplastic polyurethane resin.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a resin composition capable of achieving high adhesiveness to a thermoplastic polyurethane resin layer can be provided.
Drawings
The above object, and other objects, features and advantages will be further apparent from the following preferred embodiments and the following drawings attached hereto.
Fig. 1 is a cross-sectional view schematically showing an example of a laminate structure according to an embodiment of the present invention.
Detailed Description
Hereinafter, embodiments of the present invention will be described. The numerical range "X to Y" means X to Y unless otherwise specified. In the present embodiment, "(meth) acrylic acid" means acrylic acid, methacrylic acid, or both acrylic acid and methacrylic acid.
1. Adhesive resin composition (P)
The adhesive resin composition (P) according to the present embodiment is used for forming a resin layer in contact with a thermoplastic polyurethane resin layer, and comprises at least one ethylene/polar monomer copolymer (a) selected from an ethylene/vinyl ester copolymer and an ethylene/unsaturated carboxylic acid ester copolymer, and a glycidyl group-containing ethylene copolymer (B) (excluding the ethylene/polar monomer copolymer (a)).
In the adhesive resin composition (P) according to the present embodiment, the content of the polar monomer in the ethylene/polar monomer copolymer (a) is 21 mass% or more, preferably 23 mass% or more, more preferably 25 mass% or more, further preferably 28 mass% or more, and particularly preferably 30 mass% or more, based on the total resin components in the adhesive resin composition (P), from the viewpoint of improving adhesiveness to the thermoplastic polyurethane resin layer and flexibility of the obtained resin layer.
The upper limit of the content of the polar monomer in the ethylene/polar monomer copolymer (a) is not particularly limited, but is preferably 55 mass% or less, more preferably 50 mass% or less, further preferably 45 mass% or less, further preferably 40 mass% or less, and particularly preferably 38 mass% or less, with respect to the total resin components in the adhesive resin composition (P), from the viewpoint of further improving the mechanical properties, heat resistance, workability, and processability of the resulting resin layer.
When the polar monomer is vinyl acetate, the content of the polar monomer can be determined, for example, according to JIS K7192: 1999, the measurement was carried out.
In addition, in the case where the polar monomer is an unsaturated carboxylic acid ester, the content of the polar monomer can be measured, for example, by an infrared absorption spectrum (IR) assigned to the unsaturated carboxylic acid ester. For example, when the unsaturated carboxylic acid ester is Ethyl Acrylate (EA), 860cm of the unsaturated carboxylic acid ester is included in the EA-1The absorbance of (A) was determined. Wherein EA concentration was determined by nuclear magnetic resonance spectroscopy (NMR) and 860cm of IR was used-1The standard curve was obtained from the correlation of the absorbance of (A).
In the present embodiment, the total resin components in the adhesive resin composition (P) are the total amount of resin components such as the ethylene/polar monomer copolymer (a), the glycidyl group-containing ethylene copolymer (B), the ethylene/polar monomer copolymer (C) described later, and resins contained in other components.
In addition, in the case where the adhesive resin composition (P) according to the present embodiment further includes an ethylene/polar monomer copolymer (C) described later, from the viewpoint of further improving the adhesiveness to the thermoplastic polyurethane resin layer and the flexibility of the obtained resin layer, the total content of the polar monomer in the ethylene/polar monomer copolymer (a), the glycidyl group-containing ethylene copolymer (B), and the ethylene/polar monomer copolymer (C) is preferably 21 mass% or more, more preferably 23 mass% or more, further preferably 25 mass% or more, further preferably 28 mass% or more, and particularly preferably 30 mass% or more, with respect to the total resin components in the adhesive resin composition (P).
The upper limit of the total content of the polar monomer is not particularly limited, and is preferably 55 mass% or less, more preferably 50 mass% or less, further preferably 45 mass% or less, further preferably 40 mass% or less, and particularly preferably 38 mass% or less, with respect to the total resin components in the adhesive resin composition (P), from the viewpoint of further improving the mechanical properties, heat resistance, workability, and processability of the resulting resin layer.
According to the research of the inventor of the present application, it is confirmed that: a polyurethane-based multilayer film obtained by providing a resin layer composed of an ethylene/polar monomer copolymer on a thermoplastic polyurethane resin layer has low interlayer adhesiveness and poor workability.
Further, according to the studies of the inventors of the present application, it was confirmed that: when the content of the polar monomer in the ethylene-polar monomer copolymer is increased in order to improve the interlayer adhesiveness between the thermoplastic polyurethane resin layer and the ethylene-polar monomer copolymer layer, the interlayer adhesiveness is improved to some extent, but it is still not sufficiently satisfactory.
That is, the present inventors have found that the interlayer adhesiveness between the thermoplastic polyurethane resin layer and the ethylene/polar monomer copolymer layer cannot be obtained at a high level only by adjusting the polar monomer content in the ethylene/polar monomer copolymer.
From the above, the present inventors have found that a conventional polyurethane multilayer film has room for improvement from the viewpoint of improving the interlayer adhesiveness between the thermoplastic polyurethane resin layer and the ethylene/polar monomer copolymer layer at a high level.
The present inventors have made extensive studies to achieve the above object. As a result, they have found that a resin composition which can achieve high adhesiveness to a thermoplastic polyurethane resin layer can be obtained by using an ethylene/polar monomer copolymer (a) having a polar monomer content of not less than the lower limit value in combination with a glycidyl group-containing ethylene copolymer (B), and have completed the present invention.
That is, according to the adhesive resin composition (P) of the present embodiment, a resin layer having high adhesiveness to the thermoplastic polyurethane resin layer can be realized.
In the adhesive resin composition (P) according to the present embodiment, the total content of the ethylene/polar monomer copolymer (a) and the glycidyl group-containing ethylene copolymer (B) 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, with the total content of the adhesive resin composition (P) being 100% by mass. When the total content of the ethylene/polar monomer copolymer (a) and the content of the glycidyl group-containing ethylene copolymer (B) is within the above range, the balance among the adhesiveness, flexibility, mechanical properties, heat resistance, workability, processability, and the like of the obtained resin layer can be further improved.
In the adhesive resin composition (P) according to the present embodiment, the content of the ethylene/polar monomer copolymer (a) is preferably 50 mass% or more and 99 mass% or less, more preferably 60 mass% or more and 98 mass% or less, and particularly preferably 70 mass% or more and 97 mass% or less, with the total of the adhesive resin composition (P) being 100 mass%. When the content of the ethylene/polar monomer copolymer (a) is within the above range, the balance among adhesiveness, flexibility, mechanical properties, heat resistance, workability, processability, and the like of the obtained resin layer can be further improved.
In the adhesive resin composition (P) according to the present embodiment, the glycidyl group-containing ethylene copolymer (B) is preferably 1% by mass or more and 50% by mass or less, more preferably 2% by mass or more and 40% by mass or less, and particularly preferably 3% by mass or more and 30% by mass or less, with the total amount of the adhesive resin composition (P) being 100% by mass. When the content of the glycidyl group-containing ethylene copolymer (B) is within the above range, the balance among the adhesiveness, flexibility, mechanical properties, heat resistance, workability, processability, and the like of the obtained resin layer can be further improved.
The content of the glycidyl group is preferably 0.05% by mass or more and 10% by mass or less, more preferably 0.08% by mass or more and 8% by mass or less, still more preferably 0.1% by mass or more and 5% by mass or less, and particularly preferably 0.1% by mass or more and 1% by mass or less, with respect to 100% by mass of the total resin components in the adhesive resin composition (P).
In the adhesive resin composition (P) according to the present embodiment, the mass ratio of the content of the ethylene/polar monomer copolymer (a) to the content of the glycidyl group-containing ethylene copolymer (B) in the adhesive resin composition (P) is preferably 1 or more and 30 or less, and more preferably 5 or more and 25 or less. This makes it possible to obtain a resin layer having a better balance among adhesiveness, flexibility, mechanical properties, heat resistance, workability, processability, and the like.
The adhesive resin composition (P) according to the present embodiment preferably has a flexural modulus of rigidity, measured at a temperature of 23 ℃ according to JIS K7106, of 40MPa or less, more preferably 30MPa or less, and particularly preferably 20MPa or less. When the flexural rigidity modulus satisfies the above range, the balance among adhesiveness, flexibility, workability, processability, and the like of the obtained resin layer can be further improved. In order to realize such a flexural modulus, the composition of the adhesive resin composition (P) may be appropriately adjusted.
The lower limit of the flexural modulus is not particularly limited, but is preferably 1MPa or more, and more preferably 2MPa or more, from the viewpoint of improving heat resistance and mechanical properties.
In the adhesive resin composition (P) according to the present embodiment, the content of the carboxylic acid-modified resin in the adhesive resin composition (P) is preferably 4% by mass or less, more preferably 1% by mass or less, even more preferably 0.5% by mass or less, even more preferably 0.1% by mass or less, and particularly preferably 0.05% by mass or less, when the total amount of the adhesive resin composition (P) is 100% by mass. The carboxyl group in the carboxylic acid-modified resin may react with the glycidyl group in the glycidyl group-containing vinyl copolymer (B) to form a gel. Therefore, if the content of the carboxylic acid-modified resin in the adhesive resin composition (P) is not more than the upper limit, the following can be suppressed: the adhesive resin composition (P) is gelled during processing and preparation; aggregates are generated in the obtained resin layer.
Examples of the carboxylic acid-modified resin include modified polyolefin resins obtained by grafting or copolymerizing an unsaturated carboxylic acid or a derivative thereof with a polyolefin resin such as a polyethylene resin or a polypropylene resin.
The components constituting the adhesive resin composition (P) will be described below.
< ethylene-polar monomer copolymer (A) >
The ethylene/polar monomer copolymer according to the present embodiment includes 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 refers to a monomer having a functional group.
As the ethylene/vinyl ester copolymer according to the present embodiment, for example, one or two or more selected from an ethylene/vinyl acetate copolymer, an ethylene/vinyl propionate copolymer, an ethylene/vinyl butyrate copolymer, an ethylene/vinyl stearate copolymer, and the like 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 formed from an alkyl ester of an unsaturated carboxylic acid and ethylene may 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 anhydride, itaconic acid, and itaconic anhydride.
Examples of the alkyl moiety in the alkyl ester of the unsaturated carboxylic acid include alkyl groups having 1 to 12 carbon atoms, and more specifically, alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, 2-ethylhexyl, and isooctyl can be given. In the present embodiment, the number of carbon atoms in the alkyl portion of the alkyl ester is preferably 1 to 8.
The unsaturated carboxylic acid ester preferably contains one or more kinds selected from (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, isobutyl (meth) acrylate, n-butyl (meth) acrylate, isooctyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. These unsaturated carboxylic acid esters may be used alone or in combination of two or more. Among them, one or more selected from methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, isobutyl (meth) acrylate, n-butyl (meth) acrylate and the like are more preferably contained.
In the present embodiment, the ethylene/unsaturated carboxylic acid ester copolymer is preferably an ethylene- (meth) acrylate copolymer. Among them, a copolymer containing a compound as a (meth) acrylate is preferable. Examples of such copolymers include ethylene methyl (meth) acrylate copolymer, ethylene ethyl (meth) acrylate copolymer, ethylene isopropyl (meth) acrylate copolymer, ethylene n-propyl (meth) acrylate copolymer, ethylene isobutyl (meth) acrylate copolymer, ethylene n-butyl (meth) acrylate copolymer, ethylene isooctyl (meth) acrylate copolymer, and ethylene 2-ethylhexyl (meth) acrylate copolymer.
The ethylene/polar monomer copolymer (a) preferably contains one or more selected from the group consisting of an ethylene/vinyl acetate copolymer, an ethylene/methyl (meth) acrylate copolymer, an ethylene/ethyl (meth) acrylate copolymer, an ethylene/isopropyl (meth) acrylate copolymer, an ethylene/n-propyl (meth) acrylate copolymer, an ethylene/isobutyl (meth) acrylate copolymer and an ethylene/n-butyl (meth) acrylate copolymer, and more preferably contains an ethylene/vinyl acetate copolymer.
In the present embodiment, the ethylene/polar monomer copolymer (a) may be used alone or in combination of two or more.
In the present embodiment, from the viewpoint of further improving the processing stability, the heat resistance is measured in accordance with JIS K7210: 1999. the Melt Flow Rate (MFR) of the ethylene/polar monomer copolymer (A) measured at 190 ℃ under a load of 2160g is preferably 0.1g/10 min to 150g/10 min, more preferably 0.2g/10 min to 100g/10 min, and still more preferably 0.5g/10 min to 50g/10 min.
The MFR of the ethylene/polar monomer copolymer (A) can be adjusted by blending a plurality of ethylene/polar monomer copolymers (A) having different MFR.
The method for producing the ethylene/polar monomer copolymer (a) according to the present embodiment is not particularly limited, and it can be produced by a known method. For example, the copolymer can be obtained by radical copolymerization of the respective polymerization components at high temperature and high pressure. Further, a commercially available product can be used as the ethylene/polar monomer copolymer (A).
< glycidyl group-containing ethylene copolymer (B) >
Examples of the glycidyl group-containing ethylene copolymer (B) according to the present embodiment include one or more selected from the group consisting of an ethylene glycidyl (meth) acrylate copolymer, an ethylene glycidyl (meth) acrylate-vinyl acetate copolymer, an ethylene glycidyl (meth) acrylate- (meth) acrylate copolymer, and the like.
The content ratio of the structural unit derived from glycidyl (meth) acrylate in the glycidyl group-containing ethylene copolymer (B) is preferably 2% by mass or more and 30% by mass or less, and more preferably 3% by mass or more and 25% by mass or less.
When the content ratio of the structural unit derived from glycidyl (meth) acrylate is within the above range, the balance of the adhesiveness, flexibility, workability, processability, and the like of the obtained resin layer can be further improved.
The term "glycidyl (meth) acrylate" means at least one or both of glycidyl methacrylate and glycidyl acrylate.
The "ethylene copolymer" in the glycidyl group-containing ethylene copolymer (B) is mainly composed of an ethylene-derived structural unit. The term "main component" as used herein means that the content of the "structural unit derived from ethylene" in the whole structural units is the largest. For example, in the case of a copolymer formed from structural units derived from ethylene, glycidyl (meth) acrylate, and vinyl acetate, respectively, it means that the ratio of the structural units derived from ethylene is larger than the structural units derived from glycidyl (meth) acrylate, and the structural units derived from vinyl acetate.
The proportion of the "ethylene-derived structural unit" in the glycidyl group-containing ethylene-based copolymer (B) is preferably 65% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more. In this case, the ethylene copolymer may contain other monomer units (for example, vinyl acetate, (meth) acrylic acid ester, etc.) other than ethylene and glycidyl (meth) acrylate.
Specifically, examples of the copolymer include a copolymer containing not only the two kinds of structural units described above but also at least one of a structural unit derived from vinyl acetate and a structural unit derived from (meth) acrylic acid ester, in addition to a structural unit derived from ethylene and a structural unit derived from glycidyl (meth) acrylate.
The content ratio of the vinyl acetate-derived structural unit and the (meth) acrylate-derived structural unit is preferably 30% by mass or less, and more preferably 20% by mass or less.
The lower limit of the content ratio of the vinyl acetate-derived structural unit and the (meth) acrylate-derived structural unit is not particularly limited, and is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1% by mass or more. The content ratio of the vinyl acetate-derived structural unit or the (meth) acrylate-derived structural unit is preferably in the range of 0.1 to 30% by mass, more preferably in the range of 0.5 to 20% by mass, and particularly preferably in the range of 1 to 20% by mass.
The glycidyl group-containing ethylene copolymer (B) may be used alone, or two or more copolymers having different copolymerization ratios or two or more copolymers having different monomer species may be used in combination.
It is preferable that at least a part of the glycidyl group-containing vinyl copolymer (B) is modified with a silane coupling agent. This can improve the adhesion to the thermoplastic polyurethane resin layer.
In the adhesive resin composition (P) according to the present embodiment, the silane coupling agent in the glycidyl group-containing ethylene copolymer (B) preferably contains one or more selected from the group consisting of 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.
Here, the modification of the glycidyl group-containing vinyl copolymer (B) with the silane coupling agent includes, for example, the following methods: a method in which the glycidyl group-containing ethylene copolymer (B) is reacted with a silane coupling agent having an amino group or an epoxy group under heating (for example, 100 to 200 ℃) (modification method 1); a method of graft-polymerizing a silane coupling agent having a polymerizable group and a glycidyl group-containing vinyl copolymer (B) using a polymerization initiator (modification method 2); and so on.
In modification method 1, the silane coupling agent is introduced into the side chain of the glycidyl group-containing ethylene copolymer (B) by reacting the glycidyl group in the glycidyl group-containing ethylene copolymer (B) with the amino group or epoxy group in the silane coupling agent.
In modification method 2, the glycidyl group-containing vinyl copolymer (B), the silane coupling agent having a polymerizable group, and the radical polymerization initiator are melt-kneaded at a temperature not lower than the melting point of the glycidyl group-containing vinyl copolymer (B) and not lower than the decomposition temperature of the radical polymerization initiator, for example, using an extruder, a kneader, a banbury mixer, or the like. These reactions may be carried out in solution.
As the polymerization initiator, a commonly used polymerization initiator can be used, but an organic peroxide is preferable.
As the organic peroxide, known organic peroxides which can be used as a polymerization initiator can be used, and specific examples thereof include diacyl peroxide compounds, alkyl peroxyester compounds, peroxydicarbonate compounds, peroxycarbonate compounds, peroxyketal compounds, dialkyl peroxide compounds, hydroperoxide compounds, ketone peroxide compounds, and the like.
Among these compounds, dialkyl peroxide compounds are preferable, and 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, 1, 3-di (2-t-butylperoxyisopropyl) benzene, di-t-butyl peroxide, and 2, 5-dimethyl-2, 5-di (t-butylperoxy) -3-hexyne are more preferable.
Examples of the silane coupling agent having a polymerizable group include vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, and 3-acryloxypropyltriethoxysilane.
Examples of the silane coupling agent having an amino group include hydrochloride of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, and the like.
Examples of the silane coupling agent having an epoxy group include 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane.
In the present embodiment, from the viewpoint of further improving the processing stability, the heat resistance is measured in accordance with JIS K7210: 1999. the Melt Flow Rate (MFR) of the glycidyl group-containing ethylene copolymer (B) measured at 190 ℃ under a load of 2160g is preferably 0.1g/10 min to 50g/10 min, more preferably 0.5g/10 min to 30g/10 min, and still more preferably 1g/10 min to 20g/10 min.
The polymerization initiator for modification may be contained in an amount of usually 0.1 to 5 parts by mass, preferably 0.5 to 3 parts by mass, based on 100 parts by mass of the glycidyl group-containing ethylene copolymer (B).
The silane coupling agent may be contained in an amount of usually 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 (B). When the silane coupling agent is contained in the above range, the adhesiveness with the thermoplastic polyurethane resin layer can be further improved.
< ethylene-polar monomer copolymer (C) >
The adhesive resin composition (P) according to the present embodiment preferably further contains an ethylene/polar monomer copolymer (C) modified with a silane coupling agent. This can improve the adhesion to the thermoplastic polyurethane resin layer.
Examples of the ethylene/polar monomer copolymer in the ethylene/polar monomer copolymer (C) according to the present embodiment include an ethylene/vinyl ester copolymer, an ethylene/unsaturated carboxylic acid ester copolymer, and the like.
As the ethylene/vinyl ester copolymer, one or more selected from ethylene/vinyl acetate copolymer, ethylene/vinyl propionate copolymer, ethylene/vinyl butyrate copolymer, ethylene/vinyl stearate copolymer, and the like 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 of ethylene and an alkyl ester of an 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 anhydride, itaconic acid, and itaconic anhydride.
Examples of the alkyl moiety in the alkyl ester of the unsaturated carboxylic acid include alkyl groups having 1 to 12 carbon atoms, and more specifically, alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, 2-ethylhexyl, and isooctyl can be given. In the present embodiment, the number of carbon atoms in the alkyl portion of the alkyl ester is preferably 1 to 8.
The unsaturated carboxylic acid ester preferably contains one or more kinds selected from (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, isobutyl (meth) acrylate, n-butyl (meth) acrylate, isooctyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. These unsaturated carboxylic acid esters may be used alone or in combination of two or more. Among them, one or more selected from methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-propyl (meth) acrylate, isobutyl (meth) acrylate, n-butyl (meth) acrylate and the like are more preferably contained.
In the present embodiment, the ethylene/unsaturated carboxylic acid ester copolymer is preferably an ethylene- (meth) acrylate copolymer. Among them, a copolymer containing a compound as a (meth) acrylate is preferable. Examples of such copolymers include ethylene methyl (meth) acrylate copolymer, ethylene ethyl (meth) acrylate copolymer, ethylene isopropyl (meth) acrylate copolymer, ethylene n-propyl (meth) acrylate copolymer, ethylene isobutyl (meth) acrylate copolymer, ethylene n-butyl (meth) acrylate copolymer, ethylene isooctyl (meth) acrylate copolymer, and ethylene 2-ethylhexyl (meth) acrylate copolymer.
The ethylene/polar monomer copolymer in the ethylene/polar monomer copolymer (C) preferably contains one or more selected from the group consisting of an ethylene/vinyl acetate copolymer, an ethylene/methyl (meth) acrylate copolymer, an ethylene/ethyl (meth) acrylate copolymer, an ethylene/isopropyl (meth) acrylate copolymer, an ethylene/n-propyl (meth) acrylate copolymer, an ethylene/isobutyl (meth) acrylate copolymer and an ethylene/n-butyl (meth) acrylate copolymer, and more preferably contains an ethylene/vinyl acetate copolymer.
In the present embodiment, the ethylene/polar monomer copolymer (C) may be used alone or in combination of two or more.
The content of the polar monomer in the ethylene/polar monomer copolymer (C) is preferably 5% by mass or more and 50% by mass or less, more preferably 8% by mass or more and 45% by mass or less, and 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 determined, for example, according to JIS K7192: 1999, the measurement was carried out. In addition, in the case where the polar monomer is an unsaturated carboxylic acid ester, the content of the polar monomer can be measured, for example, by an infrared absorption spectrum (IR) assigned to the unsaturated carboxylic acid ester. For example, when the unsaturated carboxylic acid ester is Ethyl Acrylate (EA), 860cm of the unsaturated carboxylic acid ester is included in the EA-1The absorbance of (A) was determined. Wherein EA concentration was determined by nuclear magnetic resonance spectroscopy (NMR) and 860cm of IR was used-1The standard curve was obtained from the correlation of the absorbance of (A).
In the present embodiment, from the viewpoint of further improving the processing stability, the heat resistance is measured in accordance with JIS K7210: 1999. the Melt Flow Rate (MFR) of the ethylene/polar monomer copolymer (C), measured at 190 ℃ under a load of 2160g, is preferably 0.1g/10 min to 300g/10 min, more preferably 0.2g/10 min to 200g/10 min, and still more preferably 0.5g/10 min to 180g/10 min.
The MFR of the ethylene/polar monomer copolymer (C) can be adjusted by blending a plurality of ethylene/polar monomer copolymers (C) having different MFR.
The method for producing the ethylene/polar monomer copolymer in the ethylene/polar monomer copolymer (C) according to the present embodiment is not particularly limited, and the ethylene/polar monomer copolymer can be produced by a known method. For example, the copolymer can be obtained by radical copolymerization of the respective polymerization components at high temperature and high pressure. In addition, as the ethylene/polar monomer copolymer in the ethylene/polar monomer copolymer (C), a commercially available product can be used.
At least a part of the ethylene/polar monomer copolymer (C) is modified with a silane coupling agent. This can improve the adhesion to the thermoplastic polyurethane resin layer.
Here, the silane coupling agent in the ethylene-polar monomer copolymer (C) according to the present embodiment preferably includes one or more selected from the group consisting of 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.
Examples of the modification of the ethylene/polar monomer copolymer (C) with the silane coupling agent include the same methods as those for the modification of the glycidyl group-containing ethylene copolymer (B) with the silane coupling agent described above.
Further, the modification of the ethylene/polar monomer copolymer (C) with the silane coupling agent and the modification of the glycidyl group-containing ethylene copolymer (B) with the silane coupling agent may be carried out simultaneously.
When the ethylene/polar monomer copolymer (C) is modified with the silane coupling agent and the glycidyl group-containing ethylene copolymer (B) is modified with the silane coupling agent at the same time, the polymerization initiator for modification may be contained in an amount of usually 0.1 to 5 parts by mass, preferably 0.2 to 3 parts by mass, based on 100 parts by mass of the total of the glycidyl group-containing ethylene copolymer (B) and the ethylene/polar monomer copolymer (C).
The silane coupling agent may be contained in an amount of usually 5 parts by mass or less, preferably 0.02 to 3 parts by mass, based on 100 parts by mass of the total of the glycidyl group-containing ethylene copolymer (B) and the ethylene/polar monomer copolymer (C). When the silane coupling agent is contained in the above range, the adhesiveness with the thermoplastic polyurethane resin layer can be further improved.
The content of the silane coupling agent is preferably 0.01 mass% or more and 2 mass% or less, and more preferably 0.05 mass% or more and 1.0 mass% or less, with the total resin components in the adhesive resin composition (P) being 100 mass%. The content of the silane coupling agent also includes a silane coupling agent grafted to the glycidyl group-containing vinyl copolymer (B) and the ethylene/polar monomer copolymer (C).
< other ingredients >
The adhesive resin composition (P) according to the present embodiment may contain a resin and an additive other than the ethylene/polar monomer copolymer (a), the glycidyl group-containing ethylene copolymer (B), and the ethylene/polar monomer copolymer (C) within a range not to impair the effects of the present invention.
The other resin is not particularly limited, and examples thereof include polyethylene, polypropylene, and polybutylene. The additives are not particularly limited, and examples thereof include plasticizers, antioxidants, ultraviolet absorbers, antistatic agents, surfactants, colorants, light stabilizers, foaming agents, lubricants, crystal nucleating agents, crystallization accelerators, crystallization inhibitors, catalyst deactivators, inorganic fillers, organic fillers, impact resistance improvers, slip agents, crosslinking aids, adhesion promoters, silane coupling agents, processing aids, mold release agents, hydrolysis inhibitors, heat stabilizers, antiblocking agents, antifogging agents, flame retardants, flame retardant aids, heat dissipating agents, light diffusing agents, antibacterial agents, antifungal agents, and dispersants. The other components may be used alone or in combination of two or more.
< method for producing adhesive resin composition (P) >
The method for producing the adhesive resin composition (P) is not particularly limited, and for example, the following methods can be applied: a method in which the ethylene/polar monomer copolymer (a), the glycidyl group-containing ethylene copolymer (B), the ethylene/polar monomer copolymer (C) added as needed, another resin, and additives are dry blended and mixed to prepare a mixture; a method in which the ethylene/polar monomer copolymer (a), the glycidyl group-containing ethylene copolymer (B), the ethylene/polar monomer copolymer (C) added as needed, another resin, and an additive are melt-kneaded by an extruder to prepare a copolymer; and so on.
2. Laminated body
As shown in fig. 1, the laminate 10 according to the present embodiment includes at least a thermoplastic polyurethane resin layer 15 and a resin layer 20, and the resin layer 20 is provided on at least one surface of the thermoplastic polyurethane resin layer 15 and is composed of the adhesive resin composition (P) according to the present embodiment.
The thickness of the thermoplastic polyurethane resin layer 15 is, for example, 10 μm or more and 1000 μm or less.
The thickness of the resin layer 20 is, for example, 10 μm or more and 1000 μm or less.
The thermoplastic polyurethane resin constituting the thermoplastic polyurethane resin layer 15 is not particularly limited, and known resins can be used. Examples thereof include block copolymers having a hard segment of polyurethane, and a soft segment of polyester such as polyether, adipate polyester, and caprolactone polyester, and polycarbonate.
Of these, from the viewpoint of further improving the adhesiveness between the thermoplastic polyurethane resin layer 15 and the resin layer 20, a block copolymer (also referred to as a polyether-based thermoplastic polyurethane elastomer) having polyurethane as a hard segment and polyether as a soft segment is preferable as the thermoplastic polyurethane resin constituting the thermoplastic polyurethane resin layer 15.
The laminate 10 according to the present embodiment may be composed of only the thermoplastic polyurethane resin layer 15 and the resin layer 20, and may have a layer (hereinafter, also referred to as another layer) other than the thermoplastic polyurethane resin layer 15 and the resin layer 20 on the surface layer side of the resin layer 15 and/or the resin layer 20, from the viewpoint of providing various functions to the laminate 10. Examples of the other layer include a base material layer, an inorganic layer, a gas barrier layer, an antistatic layer, a hard coat layer, an adhesive layer, an antireflection layer, an anti-staining layer, a sealant layer, and an undercoat layer. The other layers may be 1 layer alone or 2 or more layers in combination.
The laminate 10 according to the present embodiment is not particularly limited, and can be suitably used as at least one selected from the group consisting of a pressure-resistant hose, a fuel pipe, a multilayer pipe, a film for clothing, a film for body fluid treatment, a medical tape, a waterproof sheet for building materials, an antifouling tape, a repair tape, and a masking tape, for example.
3. 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, a blow molding machine or the like.
This can be obtained, for example, by: an adhesive resin composition (P) containing the ethylene/polar monomer copolymer (a), the glycidyl group-containing ethylene copolymer (B), the ethylene/polar monomer copolymer (C) added as needed, other resins, and additives is supplied from a hopper of a T-die extruder, and is extruded from the tip of the T-die onto the thermoplastic polyurethane resin layer 15 to form a film shape.
In the method for producing the laminate 10 according to the present embodiment, a generally used multilayer film molding method can be applied. For example, it can be carried out by a known method using a multi-layer T-die extruder, a multi-layer inflation molding machine or the like.
This can be obtained, for example, by: an adhesive resin composition (P) comprising an ethylene/polar monomer copolymer (A), a glycidyl group-containing ethylene copolymer (B), an ethylene/polar monomer copolymer (C) added as needed, other resins, and additives, and a resin composition containing at least a thermoplastic polyurethane resin is supplied from hoppers of a main extruder and a sub-extruder of a multi-layer T-die extruder, and is formed into a sheet by coextrusion from the tip of a T-die.
While the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than the above-described configurations may be adopted.
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
The details of the components used for the preparation of the adhesive resin composition are as follows.
< ethylene-polar monomer copolymer (A) >
EVA 1: ethylene-vinyl acetate copolymer (ethylene content: 67% by mass, vinyl acetate content: 33% by mass)
EVA 2: ethylene-vinyl acetate copolymer (ethylene content: 72% by mass, vinyl acetate content: 28% by mass)
EVA 3: ethylene-vinyl acetate copolymer (ethylene content: 68% by mass, vinyl acetate content: 32% by mass)
EVA 4: ethylene-vinyl acetate copolymer (ethylene content: 60% by mass, vinyl acetate content: 40% by mass)
EVA 5: ethylene-vinyl acetate copolymer (ethylene content: 54 mass%, vinyl acetate content: 46 mass%)
EVA 6: ethylene-vinyl acetate copolymer (ethylene content: 81 mass%, vinyl acetate content: 19 mass%)
EVA 7: ethylene-vinyl acetate copolymer (ethylene content: 90% by mass, vinyl acetate content: 10% by mass)
EMA 1: ethylene/methyl methacrylate copolymer (ethylene content: 76 mass%, methyl methacrylate content: 24 mass%)
< preparation of mixture of glycidyl group-containing ethylene copolymer (B) and ethylene/polar monomer copolymer (C) modified with silane coupling agent >
An ethylene/glycidyl methacrylate/vinyl acetate copolymer (EGMAVA, manufactured by Sumitomo chemical Co., Ltd., BONDFAST 7B, ethylene content: 83 mass%, glycidyl methacrylate content: 12 mass%, vinyl acetate content: 5 mass%, MFR (190 ℃, 2160g load): 7g/10 min) 49.1 parts by mass, an ethylene/vinyl acetate copolymer (vinyl acetate content: 15 mass%), 1.5 parts by mass of 3-methacryloxypropyltrimethoxysilane (manufactured by shin-Etsu chemical Co., Ltd., trade name "KBM 503") and 0.3 part by mass of 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane (manufactured by Arkema Yoshitomi (Co., Ltd., trade name "Luperox 101") were mixed in advance, and the 3-methacryloxypropyltrimethoxysilane, a silane coupling agent, was mixed with EGMAVA and ethylene by a single screw extruder having a melt temperature of 220 ℃ C. and a diameter of 40mm The vinyl acetate copolymer is graft-modified to obtain a mixture of the glycidyl group-containing ethylene copolymer (B) and the ethylene/polar monomer copolymer (C) modified with a silane coupling agent. In table 1, the mixture is represented as a mixture of (B) and (C).
[ example 1]
A mixture of the ethylene/polar monomer copolymer (a), the glycidyl group-containing ethylene copolymer (B), and the ethylene/polar monomer copolymer (C) was fed into an extruder in the formulation shown in table 1, and melt-kneaded under the following conditions to prepare an adhesive resin composition (P), and the obtained adhesive resin composition (P) was extrusion-molded into a sheet form to prepare a resin sheet (P) having a thickness of 500 μm and made of the adhesive resin composition (P).
An extruder: 40mm profile extruder (L/D. phi. 26mm, manufactured by Nakatani Co., Ltd.)
Mixing conditions are as follows: temperature: 180 ℃, rotation speed: 60min-1
The following evaluation was performed on the obtained resin sheet (P) composed of the adhesive resin composition (P). The results are shown in table 1.
< evaluation >
(1) Evaluation of adhesion
The obtained resin sheet (P) was laminated on a thermoplastic polyurethane resin layer made of a polyether thermoplastic polyurethane elastomer (RESAMINE P-1288, manufactured by Dai purification industries, Ltd.) having a thickness of 200 μm using a vacuum heat laminator (LM-50X 50S, manufactured by NPC Co.), the resin sheet (P) was laminated on the thermoplastic polyurethane resin layer under conditions of a temperature of 170 ℃, a pressure of 0MPa (gauge pressure) and a sealing time of 2 minutes, and then the resin sheet (P) was laminated on the thermoplastic polyurethane resin layer under conditions of a temperature of 170 ℃, a pressure of 0.5MPa (gauge pressure) and a sealing time of 6 minutes. Then, the laminated body obtained by bonding was left to stand in the air and was slowly cooled by natural cooling. A 25mm wide slit (slit) was formed in the sheet portion of the completed laminate to prepare a test piece, which was set in a tensile tester. The resin sheets (P) of the laminate were separated at a draw rate of 100 mm/min, and the average value and the maximum value of the adhesive strength (N/25mm) were determined. The obtained results are shown in table 1.
(2) Flexural modulus of rigidity
The flexural modulus of the resin sheet (P) was measured at 23 ℃ in accordance with JIS K7106. The obtained results are shown in table 1.
Examples 2 to 3 and comparative examples 1 to 7
Resin sheets (P) and laminates were produced in the same manner as in example 1 except that the blending ratios shown in table 1 were set, and the same evaluations as in example 1 were performed. The obtained results are shown in table 1.
The resin sheets (P) of examples 1 to 3 had excellent adhesion to the thermoplastic polyurethane resin layer. Further, it was confirmed that even when the glycidyl group-containing ethylene copolymer (B) was included, the bending rigidity of the ethylene/polar monomer copolymer (a) was not lowered. In contrast, the resin sheets (P) of comparative examples 1 to 7 had poor adhesion to the thermoplastic polyurethane resin layer.
As can be seen from the above, the adhesive resin composition (P) according to the present embodiment can realize a resin layer having high adhesiveness to the thermoplastic polyurethane resin layer.
This application claims priority based on Japanese application laid-open at 2016, and 002508, and the entire disclosure of which is incorporated herein.
Claims (13)
1. An adhesive resin composition for forming a resin layer in contact with a thermoplastic polyurethane resin layer, the adhesive resin composition comprising:
at least one ethylene/polar monomer copolymer (A) selected from the group consisting of ethylene/vinyl ester copolymers and ethylene/unsaturated carboxylic acid ester copolymers; and
a glycidyl group-containing ethylene copolymer (B) which does not include the ethylene/polar monomer copolymer (A); and
an ethylene/polar monomer copolymer (C) modified with a silane coupling agent, the ethylene/polar monomer copolymer (C) modified with a silane coupling agent excluding the ethylene/polar monomer copolymer (A) and the glycidyl group-containing ethylene copolymer (B),
the content of the polar monomer in the ethylene-polar monomer copolymer (a) is 21 mass% or more with respect to the total resin components in the adhesive resin composition.
2. An adhesive resin composition for forming a resin layer in contact with a thermoplastic polyurethane resin layer, the adhesive resin composition comprising:
at least one ethylene/polar monomer copolymer (A) selected from the group consisting of ethylene/vinyl ester copolymers and ethylene/unsaturated carboxylic acid ester copolymers; and
a glycidyl group-containing ethylene copolymer (B) which does not include the ethylene/polar monomer copolymer (A),
the content of the polar monomer in the ethylene-polar monomer copolymer (A) is 21 mass% or more with respect to the total resin components in the adhesive resin composition,
at least a part of the glycidyl group-containing ethylene copolymer (B) is modified with a silane coupling agent.
3. The adhesive resin composition according to claim 1, wherein the silane coupling agent-modified ethylene-polar monomer copolymer (C) comprises a silane coupling agent-modified ethylene-vinyl acetate copolymer.
4. The adhesive resin composition according to claim 1 or 3, wherein the silane coupling agent in the modification of the silane coupling agent-modified ethylene-polar monomer copolymer (C) comprises one or more selected from the group consisting of 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.
5. The adhesive resin composition according to claim 2, wherein the silane coupling agent in the modification of the glycidyl group-containing ethylene copolymer (B) comprises one or more selected from the group consisting of 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.
6. The adhesive resin composition according to any one of claims 1 to 3, wherein the mass ratio of the content of the ethylene-polar monomer copolymer (A) to the content of the glycidyl group-containing ethylene copolymer (B) in the adhesive resin composition is 1 or more and 30 or less.
7. The adhesive resin composition according to any one of claims 1 to 3, wherein the glycidyl group-containing ethylene copolymer (B) comprises one or more selected from the group consisting of an ethylene glycidyl (meth) acrylate copolymer, an ethylene glycidyl (meth) acrylate-vinyl acetate copolymer, and an ethylene glycidyl (meth) acrylate copolymer.
8. The adhesive resin composition according to any one of claims 1 to 3, wherein the ethylene-polar monomer copolymer (A) comprises an ethylene-vinyl acetate copolymer.
9. The adhesive resin composition according to any one of claims 1 to 3, wherein the content of the carboxylic acid-modified resin in the adhesive resin composition is 4% by mass or less.
10. The adhesive resin composition according to any one of claims 1 to 3, wherein a flexural modulus of rigidity measured at a temperature of 23 ℃ in accordance with JIS K7106 is 40MPa or less.
11. A laminate body, comprising:
a thermoplastic polyurethane resin layer; and
a resin layer provided on at least one surface of the thermoplastic polyurethane resin layer and composed of the adhesive resin composition according to any one of claims 1 to 10.
12. The laminate according to claim 11, wherein the laminate is selected from the group consisting of a pressure-resistant hose, a fuel pipe, a multilayer pipe, a film for clothing, a film for body fluid treatment, a medical tape, a waterproof sheet for building materials, an antifouling tape, a repair tape and a masking tape.
13. A method for producing the laminate according to claim 11 or 12, the method comprising a step of co-extruding the adhesive resin composition according to any one of claims 1 to 10 and a resin composition containing at least a thermoplastic polyurethane resin.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2016-002508 | 2016-01-08 | ||
| JP2016002508 | 2016-01-08 | ||
| PCT/JP2017/000215 WO2017119469A1 (en) | 2016-01-08 | 2017-01-06 | Adhesive resin composition, layered body, and method for manufacturing layered body |
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| WO2019117085A1 (en) * | 2017-12-15 | 2019-06-20 | 三井・デュポンポリケミカル株式会社 | Layered body |
| US11851539B2 (en) * | 2018-12-04 | 2023-12-26 | Dow Global Technologies Llc | Lamination film and adhesive therefor |
| US11345129B2 (en) * | 2019-10-21 | 2022-05-31 | Covestro Llc | Barrier laminates |
| US20210114357A1 (en) * | 2019-10-21 | 2021-04-22 | Covestro Llc | Orthopedic packaging materials |
| CN116238218A (en) * | 2022-12-01 | 2023-06-09 | 北京航玻新材料技术有限公司 | A high-performance surface cross-linked composite transparent component and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH08230119A (en) * | 1995-03-02 | 1996-09-10 | Okura Ind Co Ltd | Polyurethane multilayer film |
| JPH11199679A (en) * | 1998-01-19 | 1999-07-27 | Toyo Ink Mfg Co Ltd | Wax-coated particle and utilization thereof |
| CN102006999A (en) * | 2008-02-13 | 2011-04-06 | 阿肯马法国公司 | Binder based on carboxylic acid vinyl ethylene ester copolymer and polyolefin containing a functional monomer |
| JP2011077360A (en) * | 2009-09-30 | 2011-04-14 | Asahi Kasei E-Materials Corp | Sealing resin sheet and solar cell module using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0662798B2 (en) * | 1986-02-27 | 1994-08-17 | 昭和電工株式会社 | Foam |
| JP3888309B2 (en) * | 2002-02-07 | 2007-02-28 | 住友化学株式会社 | Adhesive film and method for producing the same, and laminate and method for producing the same |
| CN101981096A (en) * | 2008-04-09 | 2011-02-23 | 旭化成电子材料株式会社 | Resin sealing sheet |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08230119A (en) * | 1995-03-02 | 1996-09-10 | Okura Ind Co Ltd | Polyurethane multilayer film |
| JPH11199679A (en) * | 1998-01-19 | 1999-07-27 | Toyo Ink Mfg Co Ltd | Wax-coated particle and utilization thereof |
| CN102006999A (en) * | 2008-02-13 | 2011-04-06 | 阿肯马法国公司 | Binder based on carboxylic acid vinyl ethylene ester copolymer and polyolefin containing a functional monomer |
| JP2011077360A (en) * | 2009-09-30 | 2011-04-14 | Asahi Kasei E-Materials Corp | Sealing resin sheet and solar cell module using the same |
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| JP6743055B2 (en) | 2020-08-19 |
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