WO2017037524A1 - Adhesive resin composition, production method for adhesive, adhesive, adhesive laminate, and laminate - Google Patents

Adhesive resin composition, production method for adhesive, adhesive, adhesive laminate, and laminate Download PDF

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Publication number
WO2017037524A1
WO2017037524A1 PCT/IB2016/001085 IB2016001085W WO2017037524A1 WO 2017037524 A1 WO2017037524 A1 WO 2017037524A1 IB 2016001085 W IB2016001085 W IB 2016001085W WO 2017037524 A1 WO2017037524 A1 WO 2017037524A1
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WO
WIPO (PCT)
Prior art keywords
adhesive
layer
laminate
component
acid
Prior art date
Application number
PCT/IB2016/001085
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French (fr)
Japanese (ja)
Inventor
邦浩 武井
悠以子 丸山
宏和 飯塚
Original Assignee
藤森工業株式会社
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Publication of WO2017037524A1 publication Critical patent/WO2017037524A1/en

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Classifications

    • 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
    • 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
    • C09J123/26—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 modified by chemical after-treatment
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C09J163/04—Epoxynovolacs
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers

Definitions

  • the present invention is formed from an adhesive having excellent adhesion to various adherends, particularly a metal, a method for producing the adhesive, an adhesive resin composition that can be used as the adhesive material, and the adhesive.
  • the present invention relates to an adhesive laminate including an adhesive layer and a laminate.
  • Patent Document 1 discloses a polyolefin multilayer film containing a dibasic carboxylic acid anhydride-modified polyolefin resin having a weight average molecular weight of 15,000 to 150,000 and a solid content acid value of 100 to 300.
  • An adhesive resin composition is disclosed.
  • patent document 1 it is supposed that favorable adhesiveness can be obtained with respect to organic and inorganic materials, such as resin and a metal, by using the said composition.
  • an adhesive resin composition that requires only an acid-modified polyolefin resin as described in Patent Document 1 adhesion between the adhesive layer made of the adhesive resin composition and the adherend is good. It is possible to do depending on conditions.
  • the metal adherend is laminated through the adhesive layer, there is a problem that the durability is poor. Therefore, in the prior art, an adhesive resin composition having excellent adhesion and durability to various adherends such as metal, glass and plastic has not been known.
  • the present invention has been made in view of the above situation, and is an adhesive resin composition and an adhesive having excellent adhesion and durability to various adherends such as metal, glass, and plastic. It aims at providing a manufacturing method, an adhesive agent, an adhesive laminated body, and a laminated body.
  • the present invention employs the following configuration. That is, in the first aspect of the present invention, 90 to 99.9 parts by mass of the acid-modified polyolefin resin (A) and 0.1 to 10 parts by mass of a phenol novolac type epoxy resin (B) that is solid at room temperature. It is an adhesive resin composition characterized by containing. It is preferable to contain 95 to 99.9 parts by mass of the acid-modified polyolefin resin (A) and 0.1 to 5 parts by mass of the phenol novolac type epoxy resin (B). It is preferable that the phenol novolac epoxy resin (B) has a bisphenol A structure. The epoxy equivalent of the phenol novolac epoxy resin (B) is preferably 100 to 300.
  • the acid-modified polyolefin resin (A) is a maleic anhydride-modified polypropylene having a melting point of 100 to 180 ° C., and the melting point of the acid-modified polyolefin resin (A) is higher than the melting point of the phenol novolac epoxy resin (B).
  • the second aspect of the present invention is a method for producing an adhesive using an adhesive resin composition, wherein the acid-modified polyolefin resin (A) and the phenol novolac epoxy resin (B ) And melt-kneading.
  • the melt kneading is preferably performed under heating at 240 to 300 ° C.
  • a third aspect of the present invention is an adhesive obtained by melt-kneading an adhesive resin composition.
  • an adhesive laminate including a first adhesive layer, a base material layer, and a second adhesive layer in this order, and the first adhesive layer or the second adhesive layer. Any one or both of these are formed from the adhesive according to the third aspect of the present invention, and this is an adhesive laminate.
  • the fifth aspect of the present invention is an adhesive laminate including a first adhesive layer, a first intermediate layer, a base material layer, a second intermediate layer, and a second adhesive layer in this order, Either or both of the first adhesive layer and the second adhesive layer are formed from the adhesive according to the third aspect of the present invention, and the adhesive laminate is characterized in that it is an adhesive laminate.
  • a sixth aspect of the present invention is a laminate comprising the first metal layer, the adhesive laminate, and the second metal layer in this order.
  • the adhesive resin composition of the first aspect of the present invention comprises 90 to 99.9 parts by mass of an acid-modified polyolefin resin (A) and 0.1 to 10 parts by mass of a phenol novolac epoxy resin (B) that is solid at room temperature.
  • the acid-modified polyolefin resin (A) may be referred to as “(A) component”
  • the phenol novolac type epoxy resin (B) may be referred to as “(B) component”.
  • the acid-modified polyolefin resin (A) is a polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof, and an acid functional group such as a carboxy group or a carboxylic anhydride group in the polyolefin resin. It is what has.
  • the component (A) is obtained by modifying a polyolefin resin with an unsaturated carboxylic acid or a derivative thereof, or copolymerizing an acid functional group-containing monomer and an olefin.
  • (A) component what was obtained by acid-modifying polyolefin resin is preferable.
  • Examples of the acid modification method include graft modification in which a polyolefin resin and an acid functional group-containing monomer are melt-kneaded in the presence of a radical polymerization initiator such as an organic peroxide or an aliphatic azo compound.
  • a radical polymerization initiator such as an organic peroxide or an aliphatic azo compound.
  • polystyrene resin examples include polyethylene, polypropylene, poly-1-butene, polyisobutylene, a random copolymer of propylene and ethylene or ⁇ -olefin, and a block copolymer of propylene and ethylene or ⁇ -olefin. It is done. Among these, homopolypropylene (propylene homopolymer; hereinafter sometimes referred to as “homo PP”), propylene-ethylene block copolymer (hereinafter sometimes referred to as “block PP”), and propylene-ethylene. Polypropylene resins such as random copolymers (hereinafter sometimes referred to as “random PP”) are preferred, and random PP is particularly preferred. Examples of the olefins for copolymerization include olefinic monomers such as ethylene, propylene, 1-butene, isobutylene, 1-hexene, and ⁇ -olefin.
  • the acid functional group-containing monomer is a compound having an ethylenic double bond and a carboxy group or a carboxylic anhydride group in the same molecule, and various unsaturated monocarboxylic acids, dicarboxylic acids, or dicarboxylic acid acids.
  • Anhydrides are mentioned.
  • Acid functional group-containing monomers having carboxy groups include acrylic acid, methacrylic acid, maleic acid, nadic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, tetrahydrophthalic acid, endo - ⁇ , ⁇ -unsaturated carboxylic acid monomers such as bicyclo [2.2.1] -5-heptene-2,3-dicarboxylic acid (endic acid).
  • acid functional group-containing monomers having carboxylic anhydride groups include unsaturated dicarboxylic acids such as maleic anhydride, nadic anhydride, itaconic anhydride, citraconic anhydride, and endic anhydride An anhydride monomer is mentioned. These acid functional group-containing monomers may be used alone or in combination of two or more in the component (A).
  • the acid functional group-containing monomer is preferably an acid functional group-containing monomer having an acid anhydride group, more preferably a carboxylic acid anhydride group-containing monomer, because of its high reactivity with the component (B) described later.
  • Maleic anhydride is particularly preferred.
  • the unreacted acid functional group-containing monomer was removed in advance in order to prevent a decrease in adhesive strength due to the unreacted acid functional group-containing monomer. It is preferable to use those as the component (A).
  • the component derived from the polyolefin resin or olefin is preferably 50 parts by mass or more with respect to 100 parts by mass of the total amount of the component (A).
  • the melting point of the component (A) is preferably 100 ° C. to 180 ° C. in consideration of the temperature when the component (A) and the component (B) described later are melt-kneaded.
  • the component (A) having a melting point in the above range the component (A) and the component (B) to be described later can be obtained from the melting point of the component (A) even when a conventional method and a general apparatus are used. Can be melt-kneaded at a sufficiently high temperature.
  • the melting point of the component (B) is lower than that of the component (A).
  • the melting point of the component (A) is preferably higher than the melting point of the component (B) described later, but the melting point of the component (A) is higher by 10 ° C. than the melting point of the component (B). More preferably, it is more preferably 20 ° C. or higher, and particularly preferably 30 ° C. or higher.
  • the melting point of the component (A) is sufficiently higher than that of the component (B)
  • the component (B) is melted first when the melt kneading is performed, and the component (A) in the state where the shape of the resin is maintained. As a result of permeation and a uniform reaction between the component (A) and the component (B), good durability can be obtained.
  • maleic anhydride-modified polypropylene is preferable from the viewpoints of adhesiveness and an appropriate melting point.
  • the component (B) is a phenol novolac type epoxy resin that is solid at room temperature. Even when the component (A) and the component (B) are polymerized by melt kneading by using the component (B) that is solid at normal temperature, melt kneading is performed in accordance with the melting temperature of the component (A). In that case, the characteristics of the component (B) are hardly impaired.
  • “normal temperature” is about 3 ° C. to about 40 ° C., preferably about 10 ° C. to about 30 ° C., more preferably about 15 ° C. to about 25 ° C., and most preferably. Is about 23 ° C.
  • the phenol novolac type epoxy resin (B) is a compound in which a phenol novolac resin obtained by acid condensation of phenol and formaldehyde has a basic structure and an epoxy group is introduced into a part of the structure.
  • the amount of epoxy group introduced per molecule in the phenol novolac type epoxy resin is not particularly limited, but there are many in the phenol novolac resin by reacting an epoxy group raw material such as epichlorohydrin with the phenol novolac resin. Since many epoxy groups are introduced into the phenolic hydroxyl group, it is usually a polyfunctional epoxy resin.
  • the component (B) is preferably a resin having a phenol novolac structure as a basic skeleton and a bisphenol A structure.
  • the bisphenol A structure in (B) component should just be a structure which can be induced
  • resin represented by the following general formula (1) is mentioned.
  • R 1 to R 6 are each independently a hydrogen atom or a methyl group, n is an integer of 0 to 10, and R X is a group having an epoxy group. ]
  • R 1 to R 6 are each independently a hydrogen atom or a methyl group.
  • R 3 and R 4 may be the same or different.
  • the resin represented by the formula (1) preferably satisfies at least one of the following (i) to (iii).
  • Both R 1 and R 2 are methyl groups
  • Both R 3 and R 4 are methyl groups
  • Both R 5 and R 6 are methyl groups
  • the carbon atom to which R 1 and R 2 are bonded and the two hydroxyphenyl groups to which the carbon atom is bonded constitute a structure derived from bisphenol A.
  • R X is a group having an epoxy group.
  • the group having an epoxy group include an epoxy group, a combination of an epoxy group and an alkylene group, and among them, a glycidyl group is preferable.
  • the epoxy equivalent of the component (B) is preferably 100 to 300, and more preferably 200 to 300.
  • the epoxy equivalent (g / eq) is the molecular weight of the epoxy resin per epoxy group, and the smaller the value, the more epoxy groups in the resin.
  • component (B) jER154, jER157S70, jER-157S65 manufactured by Mitsubishi Chemical Corporation; EPICLON N-730A, EPICLON N-740, EPICLON N-770, EPICLONN-775 (all above, manufactured by DIC) Commercial products such as (trade name) can also be used.
  • both the acid functional group of the component (A) and the epoxy group of the component (B) are bonded to an adherend (particularly a functional group such as a hydroxyl group possessed by the adherend).
  • an adherend particularly a functional group such as a hydroxyl group possessed by the adherend.
  • a functional functional group By functioning as a functional functional group, it is considered that excellent adhesion to various adherends such as metal, glass, and plastic can be achieved.
  • a part of the acid functional group of the component (A) and a part of the epoxy group of the component (B) react to form a crosslinked structure of the component (A) and the component (B). It is considered that the strength of the resin is reinforced and good durability is obtained together with excellent adhesiveness.
  • the component (B) is contained in an amount of 0.1 to 10 parts by mass with respect to 90 to 99.9 parts by mass of the component (A). More preferably, the component (B) is 1 to 5% by mass with respect to 95 to 99 parts by mass of the component (A), and most preferably the component (B) with respect to 97 to 99 parts by mass of the component (A). Is 1 to 3% by mass.
  • the adhesive composition of the present invention can appropriately contain miscible additives, additional resins, plasticizers, stabilizers, colorants and the like as desired.
  • the method for producing an adhesive according to the second aspect of the present invention melts and kneads an acid-modified polyolefin resin (A) and a phenol novolac epoxy resin (B).
  • the acid-modified polyolefin resin (A) and the phenol novolac type epoxy resin (B) are the same as the component (A) and the component (B) in the first aspect described above, respectively.
  • (A) component and (B) component are made to react by melt-kneading the said adhesive resin composition containing the said (A) component and the said (B) component using a well-known apparatus. Can do.
  • a single screw extruder, a multi-screw extruder, a Banbury mixer, a plast mill, a heated roll kneader, or the like can be used.
  • the volatile component that can react with the epoxy group such as moisture is previously removed from the apparatus.
  • a volatile component is generated during the reaction, it is desirable to discharge it from the apparatus as needed by degassing or the like.
  • the acid-modified polyolefin resin (A) has an acid anhydride group as an acid functional group, it is preferable because the reactivity with the epoxy group of the component (B) is high and the reaction can be performed under milder conditions. .
  • the heating temperature at the time of melt kneading is preferably selected from the range of 240 to 300 ° C. in that the components (A) and (B) are sufficiently melted and are not thermally decomposed.
  • the kneading temperature can be measured by a method such as bringing a thermocouple into contact with the molten adhesive resin composition immediately after being extruded from the melt kneader.
  • the adhesive according to the third aspect of the present invention is obtained by melt-kneading the adhesive resin composition according to the first aspect, and the melt-kneading method is the same as in the second aspect described above. is there. Since the adhesive of the present invention is obtained from the adhesive resin composition containing the component (A) and the component (B), various adherends such as metal, glass, plastic, etc. It can be satisfactorily bonded in a state in which deterioration and environmental deterioration are suppressed.
  • the adhesive laminate of the fourth aspect of the present invention comprises a first adhesive layer, a base material layer, and a second adhesive layer in this order, and the first adhesive layer or the second adhesive layer. Either or both are formed from the adhesive of the third aspect.
  • the adhesive laminated body of the 5th aspect of this invention is the adhesion
  • the fourth and fifth adhesive laminates are laminates formed from the adhesive resin composition of the present invention and having a shape such as a film, a sheet, etc., as an adhesive resin film, an adhesive resin sheet, etc. It can be used for many purposes.
  • At least one of the first and second adhesive layers in the fourth and fifth aspects is formed from the adhesive of the third aspect, but both are from the adhesive of the third aspect. Preferably it is formed.
  • the base material layer in the fourth and fifth embodiments is not particularly limited as long as it has sufficient mechanical strength.
  • PEN polyethylene naphthalate
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PEN, COP or TPX is preferable, and COP or TPX is particularly preferable because the linear expansion coefficient is low and it is difficult to cause delamination even when an adherend such as a metal is adhered using the adhesive laminate. preferable.
  • a particulate or fibrous filler can be added as an additive to the base material layer.
  • the filler should just be a filler with high heat resistance, and an organic filler and an inorganic filler are mentioned.
  • an inorganic filler it is preferable to add an inorganic filler from the viewpoint of heat resistance and shrinkability of the base material layer.
  • carbonates such as calcium carbonate, magnesium carbonate and barium carbonate
  • sulfates such as calcium sulfate, magnesium sulfate and barium sulfate
  • chlorides such as sodium chloride, calcium chloride and magnesium chloride
  • aluminum oxide calcium oxide
  • oxides such as magnesium oxide, zinc oxide, titanium oxide, and silica
  • minerals such as talc, smectite, mica, and kaolinite
  • carbon compounds such as carbon fiber and carbon particles; and fine particles made of glass.
  • the shape include a spherical shape, a rod shape, and a plate shape, and a plate-like compound is preferable.
  • middle layer in a 5th aspect is a layer which has adhesiveness with respect to a base material layer and a 1st contact bonding layer.
  • the second intermediate layer is a layer having adhesion to the base material layer and the second adhesive layer.
  • the adhesiveness required for the first intermediate layer and the second intermediate layer refers to the strength to maintain the strength as a laminate of the base material layer and the adhesive layer. Is less likely to occur.
  • the material for forming the first intermediate layer and the second intermediate layer is not particularly limited as long as the first intermediate layer and the second intermediate layer have the above-mentioned adhesiveness. It is selected as appropriate.
  • the material for forming the base material layer is a cyclic olefin polymer (COP)
  • the material for forming the first intermediate layer and the second intermediate layer is selected from the group consisting of acid-modified polypropylene, metallocene polyethylene, and metallocene polypropylene It is preferable that it is at least one kind. That is, as a material for forming the first intermediate layer and the second intermediate layer, one kind selected from the group consisting of polypropylene, metallocene polyethylene, and metallocene polypropylene may be used alone, or two or more kinds may be used. You may use it in combination.
  • COP cyclic olefin polymer
  • the formation material of the first intermediate layer and the second intermediate layer is composed of three components of acid-modified polypropylene, metallocene-based polyethylene, and metallocene-based polypropylene
  • the compounding amount of the acid-modified polypropylene is preferably 10 to 40 parts by mass
  • the compounding amount of the metallocene polyethylene is preferably 30 to 50 parts by mass
  • the compounding amount of the metallocene polypropylene is preferably 30 to 40 parts by mass
  • the blending amount of the acid-modified polypropylene is 20 parts by weight
  • the blending amount of the metallocene-based polyethylene is 50 parts by weight
  • the blending amount of the metallocene-based polypropylene is 30 parts by weight.
  • the intermediate layer is used to form the fifth aspect of the present invention, that is, a five-layer structure of adhesive layer / intermediate layer / base material layer / intermediate layer / adhesive layer, film formation is simultaneously performed by melt extrusion flow. It is preferable to form.
  • the forming material of the base layer is methylpentene polymer (TPX)
  • the forming material of the first intermediate layer and the second intermediate layer is selected from the group consisting of methylpentene polymer, polybutene-based elastomer, and polypropylene. It is preferable that there is at least one. That is, as a material for forming the first intermediate layer and the second intermediate layer, one kind selected from the group consisting of methylpentene polymer, polybutene elastomer, and polypropylene may be used alone, or two or more kinds may be combined. May be used. An acid-modified methylpentene polymer may be used as the methylpentene polymer.
  • the material for forming the first intermediate layer and the second intermediate layer is composed of four components of methylpentene polymer, acid-modified methylpentene polymer, polybutene-based elastomer, and polypropylene, the total of these four components is 100 parts by mass.
  • the blending amount of the methylpentene polymer is 10 to 70 parts by weight, more preferably 20 to 50 parts by weight, and the blending amount of the acid-modified methylpentene polymer is 0 to 50 parts by weight, more preferably More than 0 parts by mass and 30 parts by mass or less, the blending amount of the polybutene elastomer is 5 to 40 parts by weight, more preferably 10 to 30 parts by weight, and the blending amount of polypropylene is 5 to 40 parts by weight. Is preferred.
  • the intermediate layer is used to form the fifth aspect of the present invention, that is, a five-layer structure of adhesive layer / intermediate layer / base material layer / intermediate layer / adhesive layer, film formation is simultaneously performed by melt extrusion flow. It is preferable to form.
  • the adhesive laminate includes, for example, a first adhesive layer, a base material layer, and a second adhesive layer, or a first adhesive layer, a first intermediate layer, a base material layer, a second intermediate layer, and
  • the second adhesive layer may be produced by coextrusion using an extruder; the first adhesive layer and the second adhesive layer separately melt-formed are thermally laminated on both sides of the base material layer.
  • the first and second intermediate layer materials are applied by solution and then dried to form the first and second intermediate layers; Then, you may manufacture by thermally laminating the 1st contact bonding layer and the 2nd contact bonding layer which carried out separate melt-deposition on the formed 1st and 2nd intermediate layer (5th mode).
  • the intermediate layer when the intermediate layer is provided by coating, the intermediate layer is preferably provided using an olefin-based polymer.
  • the olefin polymer is preferably polyethylene, polypropylene, or polybutene, and is preferably acid-modified with a carboxylic acid such as maleic acid.
  • the first and second adhesive layers are preferably 5 to 80 ⁇ m, more preferably 10 to 50 ⁇ m.
  • the substrate layer is preferably 50 to 300 ⁇ m, more preferably 60 to 200 ⁇ m.
  • the first intermediate layer and the second intermediate layer are preferably 5 to 20 ⁇ m when manufactured by coextrusion, and preferably 0.5 to 5 ⁇ m when manufactured by solution coating.
  • the laminated body of the 6th aspect of this invention is equipped with the 1st metal layer, the adhesive laminated body of the said 4th or 5th aspect, and the 2nd metal layer in this order. Since the adhesive layer in the adhesive laminate is formed from the adhesive resin composition of the present invention, good adhesion and durability can be obtained even when metals are bonded together. Since both surfaces of the adhesive laminate used for the sixth laminate are in contact with the metal layer, both the first and second adhesive layers are formed from the adhesive resin composition (adhesive) of the present invention. It is preferable.
  • As the first metal layer and the second metal layer which are adherends to be bonded using the laminate of the present invention generally known metal plates, metal flat plates, or metal foils can be used.
  • the metal used for these include iron, copper, aluminum, lead, zinc, titanium, and chromium, and may also be stainless steel that is an alloy.
  • it is a metal flat plate or metal foil made of iron, aluminum, titanium, stainless steel, surface-treated metal, and these can be used as the first metal layer and / or the second metal layer.
  • the adhesive layer of the invention exhibits a particularly strong adhesive force.
  • Examples 1-1 to 1-5, Comparative Examples 1-1 to 1-4] Adhesive resin film
  • the components (A) and (B) shown in Table 1 were melt-kneaded at 280 ° C. for 2 minutes, and then formed into a film having a predetermined thickness by extrusion to obtain an adhesive sheet.
  • Examples 2-1 to 2-4 (Adhesion evaluation) 98 parts by mass of (A) -1 and 2 parts by mass of (B) -1 were melt-kneaded for 2 minutes at the temperatures shown in Table 2, and then formed into a film having a predetermined thickness by extrusion. To obtain an adhesive sheet. Using the obtained adhesive sheet, a laminate was produced in the same manner as in the above-described adhesion evaluation, and a tensile shear test was conducted in the same manner as described above. The results of evaluation similar to the above evaluation criteria are also shown in Table 2.
  • Example 3-1 to 3-5 an adhesive resin composition having 98 parts by mass of (A) -1 and 2 parts by mass of (B) -1 was used.
  • Example 3-1 The adhesive composition having the component (A) and the component (B) was melt-kneaded at 280 ° C. for 2 minutes, and then co-extruded with PEN. “Adhesion layer (thickness 42 ⁇ m) -PEN substrate (thickness 75 ⁇ m) ) -Adhesive layer (thickness 42 ⁇ m) ”was obtained.
  • Example 3-2 A dispersion solution of a maleic acid-modified propylene-butene copolymer was applied on both sides of a PEN substrate having a thickness of 75 ⁇ m so as to form an intermediate layer having a thickness of 2.0 ⁇ m, and dried. Moreover, the adhesive composition having the component (A) and the component (B) was melt-kneaded at 280 ° C. for 2 minutes and then extruded to produce two adhesive films (thickness 40 ⁇ m).
  • the adhesive film obtained separately was placed on the intermediate layer provided on both sides of the PEN base material and heat laminated at 170 ° C., and “adhesive layer-intermediate layer-PEN base material-intermediate layer-adhesion” was obtained.
  • An adhesive laminate having a five-layer structure of “layer” was obtained.
  • Example 3-3 After melt-kneading the adhesive composition having the component (A) and the component (B) at 280 ° C. for 2 minutes, COP as the base material, and intermediate layer, polypropylene, metallocene polyethylene, metallocene polypropylene, and styrene heat Co-extrusion is performed together with a polymer blended with a plastic elastomer, and “adhesion layer (thickness 27 ⁇ m) —intermediate layer (thickness 15 ⁇ m) —COP substrate (thickness 75 ⁇ m) —intermediate layer (thickness 15 ⁇ m) —adhesion layer ( An adhesive laminate having a five-layer structure having a thickness of 27 ⁇ m) ”was obtained.
  • Example 3-4 After melt-kneading the adhesive composition having the component (A) and the component (B) at 280 ° C. for 2 minutes, the TPX as the base material and the mixed polymer of methylpentene polymer, polybutene and polypropylene as the intermediate layer are used together. Extrusion molding was performed, and five layers of “adhesive layer (thickness 27 ⁇ m) —intermediate layer (thickness 15 ⁇ m) —TPX substrate (thickness 75 ⁇ m) —intermediate layer (thickness 15 ⁇ m) —adhesive layer (thickness 27 ⁇ m)” An adhesive laminate having the structure was obtained.
  • Example 3-5 The adhesive composition having the component (A) and the component (B) was melt-kneaded at 280 ° C. for 2 minutes and then extruded to produce an adhesive film (thickness: 159 ⁇ m).
  • the aluminum foil having a thickness of 300 ⁇ m and a length of 30 mm ⁇ width of 30 mm is laminated with a three-layer or five-layer adhesive laminate or an adhesive film of each example cut into 30 mm ⁇ 30 mm, and the thickness is 300 ⁇ m and length is 30 mm.
  • X The end of the stainless steel foil cut out to 30 mm in width was placed, and the laminate was laminated at 150 ° C. for 5 seconds while applying a pressure of 0.5 MPa.
  • the laminate was immersed in 95 ° C. hot water for 300 hours, and the state of the laminate after immersion was observed and evaluated. The results are shown in Table 3 as “laminate strength”.
  • A There was no visible peeling, and no distortion of the laminate was observed.
  • B Visible and conspicuous, no peeling was seen, and no major distortion was seen.
  • C Some peeling or some distortion of the laminate was observed, but it was within the allowable range.
  • D Peeling was observed on the entire surface, and the laminate was distorted.

Abstract

The present invention pertains to an adhesive resin composition having excellent adhesive strength and durability, a production method for an adhesive, an adhesive, an adhesive laminate, and a laminate. More specifically, the present invention pertains to: an adhesive resin composition characterized by containing 90–99.9 parts by mass of (A) an acid-modified polyolefin resin, and 0.1–10 parts by mass of (B) a phenol novolac epoxy resin which is solid at room temperature; an adhesive characterized by being obtained by melt kneading the adhesive resin composition; an adhesive laminate provided with, in the following order, a first adhesive layer, a first intermediate layer, a substrate layer, a second intermediate layer, and a second adhesive layer, said adhesive laminate being characterized in that the first adhesive layer and/or the second adhesive layer are formed from the adhesive; and a laminate characterized by being provided with, in the following order, a first metal layer, the adhesive laminate, and a second metal layer.

Description

接着性樹脂組成物、接着剤の製造方法、接着剤、接着性積層体、及び積層体Adhesive resin composition, method for producing adhesive, adhesive, adhesive laminate, and laminate
　本発明は、各種の被着体、特に金属に対して優れた接着性を有する接着剤、当該接着剤の製造方法、当該接着剤材料として用い得る接着性樹脂組成物、当該接着剤から形成される接着層を備えた接着性積層体、及び積層体に関する。
　本願は、２０１５年８月６日に出願された日本国特願２０１５−１５６３６４号に基づく優先権を主張し、その内容をここに援用する。 The present invention is formed from an adhesive having excellent adhesion to various adherends, particularly a metal, a method for producing the adhesive, an adhesive resin composition that can be used as the adhesive material, and the adhesive. The present invention relates to an adhesive laminate including an adhesive layer and a laminate.
This application claims the priority based on Japanese Patent Application No. 2015-156364 for which it applied on August 6, 2015, and uses the content here.
　従来、金属等の被着体に接着する材料として、酸変性ポリオレフィン樹脂を有するホットメルト接着剤が知られている。
　例えば、特許文献１には、重量平均分子量が１５，０００~１５０，０００であり、固形分酸価が１００~３００である、二塩基カルボン酸無水物変性ポリオレフィン樹脂を含有する、ポリオレフィン多層フィルム用接着性樹脂組成物が開示されている。 Conventionally, a hot melt adhesive having an acid-modified polyolefin resin is known as a material that adheres to an adherend such as metal.
For example, Patent Document 1 discloses a polyolefin multilayer film containing a dibasic carboxylic acid anhydride-modified polyolefin resin having a weight average molecular weight of 15,000 to 150,000 and a solid content acid value of 100 to 300. An adhesive resin composition is disclosed.
　特許文献１では、当該組成物を用いることにより、樹脂及び金属等の有機・無機材料に対して良好な接着性を得ることができるとしている。確かに、特許文献１に記載のような酸変性ポリオレフィン樹脂のみを必須とする接着性樹脂組成物を用いた場合、接着性樹脂組成物からなる接着剤層と被着体との接着を良好とすることは条件によっては可能である。しかしながら、当該接着剤層を介して金属被着体の積層を行った場合、耐久性に劣るという問題があった。
　そのため、従来技術においては、金属、ガラス、プラスチックなどの各種の被着体に対して、優れた接着性及び耐久性を有する接着剤樹脂組成物は知られていなかった。 In patent document 1, it is supposed that favorable adhesiveness can be obtained with respect to organic and inorganic materials, such as resin and a metal, by using the said composition. Certainly, when using an adhesive resin composition that requires only an acid-modified polyolefin resin as described in Patent Document 1, adhesion between the adhesive layer made of the adhesive resin composition and the adherend is good. It is possible to do depending on conditions. However, when the metal adherend is laminated through the adhesive layer, there is a problem that the durability is poor.
Therefore, in the prior art, an adhesive resin composition having excellent adhesion and durability to various adherends such as metal, glass and plastic has not been known.
日本国特開２０１２−００１６６１号公報Japanese Unexamined Patent Publication No. 2012-001661
　本発明は、上記現状に鑑みてなされたものであって、金属、ガラス、プラスチックなどの各種の被着体に対して、優れた接着力及び耐久性を有する接着性樹脂組成物、接着剤の製造方法、接着剤、接着性積層体、及び積層体を提供することを目的とする。 The present invention has been made in view of the above situation, and is an adhesive resin composition and an adhesive having excellent adhesion and durability to various adherends such as metal, glass, and plastic. It aims at providing a manufacturing method, an adhesive agent, an adhesive laminated body, and a laminated body.
　上記の課題を解決するために、本発明は以下の構成を採用した。
　すなわち、本発明の第一の態様は、酸変性ポリオレフィン樹脂（Ａ）９０~９９．９質量部と、常温で固体であるフェノールノボラック型エポキシ樹脂（Ｂ）０．１~１０質量部と、を含有することを特徴とする接着性樹脂組成物である。
　前記酸変性ポリオレフィン樹脂（Ａ）９５~９９．９質量部と、前記フェノールノボラック型エポキシ樹脂（Ｂ）０．１~５質量部と、を含有することが好ましい。
　前記フェノールノボラック型エポキシ樹脂（Ｂ）が、ビスフェノールＡ構造を有するものであることが好ましい。
　前記フェノールノボラック型エポキシ樹脂（Ｂ）のエポキシ当量が、１００~３００であることが好ましい。
　前記酸変性ポリオレフィン樹脂（Ａ）は、融点が１００~１８０℃の無水マレイン酸変性ポリプロピレンであって、前記酸変性ポリオレフィン樹脂（Ａ）の融点が、前記フェノールノボラック型エポキシ樹脂（Ｂ）の融点よりも高いことが好ましい
　本発明の第二の態様は、接着性樹脂組成物を用いて接着剤を製造する方法であって、前記酸変性ポリオレフィン樹脂（Ａ）と、前記フェノールノボラック型エポキシ樹脂（Ｂ）とを溶融混練することを特徴とする接着剤の製造方法である。
　前記溶融混練が２４０~３００℃の加熱下で行われることが好ましい。
　本発明の第三の態様は、接着性樹脂組成物を溶融混練して得られることを特徴とする接着剤である。
　本発明の第四の態様は、第１の接着層、基材層、及び第２の接着層をこの順に備えた接着性積層体であって、前記第１の接着層又は第２の接着層のいずれか一方又は両方が、本発明の第三の態様に記載の接着剤から形成されることを特徴とする接着性積層体である。
　本発明の第五の態様は、第１の接着層、第１の中間層、基材層、第２の中間層、及び第２の接着層をこの順に備えた接着性積層体であって、前記第１の接着層又は第２の接着層のいずれか一方又は両方が、本発明の第三の態様に記載の接着剤から形成されることを特徴とする接着性積層体である。
　本発明の第六の態様は、第１の金属層、前記接着性積層体、及び第２の金属層をこの順に備えることを特徴とする積層体である。 In order to solve the above problems, the present invention employs the following configuration.
That is, in the first aspect of the present invention, 90 to 99.9 parts by mass of the acid-modified polyolefin resin (A) and 0.1 to 10 parts by mass of a phenol novolac type epoxy resin (B) that is solid at room temperature. It is an adhesive resin composition characterized by containing.
It is preferable to contain 95 to 99.9 parts by mass of the acid-modified polyolefin resin (A) and 0.1 to 5 parts by mass of the phenol novolac type epoxy resin (B).
It is preferable that the phenol novolac epoxy resin (B) has a bisphenol A structure.
The epoxy equivalent of the phenol novolac epoxy resin (B) is preferably 100 to 300.
The acid-modified polyolefin resin (A) is a maleic anhydride-modified polypropylene having a melting point of 100 to 180 ° C., and the melting point of the acid-modified polyolefin resin (A) is higher than the melting point of the phenol novolac epoxy resin (B). The second aspect of the present invention is a method for producing an adhesive using an adhesive resin composition, wherein the acid-modified polyolefin resin (A) and the phenol novolac epoxy resin (B ) And melt-kneading.
The melt kneading is preferably performed under heating at 240 to 300 ° C.
A third aspect of the present invention is an adhesive obtained by melt-kneading an adhesive resin composition.
According to a fourth aspect of the present invention, there is provided an adhesive laminate including a first adhesive layer, a base material layer, and a second adhesive layer in this order, and the first adhesive layer or the second adhesive layer. Any one or both of these are formed from the adhesive according to the third aspect of the present invention, and this is an adhesive laminate.
The fifth aspect of the present invention is an adhesive laminate including a first adhesive layer, a first intermediate layer, a base material layer, a second intermediate layer, and a second adhesive layer in this order, Either or both of the first adhesive layer and the second adhesive layer are formed from the adhesive according to the third aspect of the present invention, and the adhesive laminate is characterized in that it is an adhesive laminate.
A sixth aspect of the present invention is a laminate comprising the first metal layer, the adhesive laminate, and the second metal layer in this order.
　本発明によれば、金属、ガラス、プラスチック等の各種の被着体に対して、優れた接着性及び耐久性を有する接着性樹脂組成物、接着剤の製造方法、接着剤、接着性積層体、及び積層体を得ることが可能となる。 ADVANTAGE OF THE INVENTION According to this invention, with respect to various adherends, such as a metal, glass, a plastic, the adhesive resin composition which has the outstanding adhesiveness and durability, the manufacturing method of an adhesive agent, an adhesive agent, and an adhesive laminated body And a laminated body can be obtained.
　以下、好適な実施の形態に基づき、本発明を説明する。 Hereinafter, the present invention will be described based on preferred embodiments.
［接着性樹脂組成物］
　本発明の第一の態様の接着性樹脂組成物は、酸変性ポリオレフィン樹脂（Ａ）９０~９９．９質量部と、常温で固体であるフェノールノボラック型エポキシ樹脂（Ｂ）０．１~１０質量部と、を含有するものである。
　以下、酸変性ポリオレフィン樹脂（Ａ）を「（Ａ）成分」、フェノールノボラック型エポキシ樹脂（Ｂ）を「（Ｂ）成分」ということがある。 [Adhesive resin composition]
The adhesive resin composition of the first aspect of the present invention comprises 90 to 99.9 parts by mass of an acid-modified polyolefin resin (A) and 0.1 to 10 parts by mass of a phenol novolac epoxy resin (B) that is solid at room temperature. Part.
Hereinafter, the acid-modified polyolefin resin (A) may be referred to as “(A) component”, and the phenol novolac type epoxy resin (B) may be referred to as “(B) component”.
（酸変性ポリオレフィン樹脂（Ａ））
　本発明において、酸変性ポリオレフィン樹脂（Ａ）とは、不飽和カルボン酸又はその誘導体で変性されたポリオレフィン系樹脂であって、ポリオレフィン系樹脂中に、カルボキシ基又は無水カルボン酸基等の酸官能基を有するものである。
　（Ａ）成分は、不飽和カルボン酸又はその誘導体によるポリオレフィン系樹脂の変性、或いは酸官能基含有モノマーとオレフィン類との共重合等により得られる。なかでも（Ａ）成分としては、ポリオレフィン系樹脂を酸変性して得られたものが好ましい。
　酸変性方法としては、有機過酸化物又は脂肪族アゾ化合物等のラジカル重合開始剤の存在下で、ポリオレフィン樹脂と酸官能基含有モノマーとを溶融混練するグラフト変性が挙げられる。 (Acid-modified polyolefin resin (A))
In the present invention, the acid-modified polyolefin resin (A) is a polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof, and an acid functional group such as a carboxy group or a carboxylic anhydride group in the polyolefin resin. It is what has.
The component (A) is obtained by modifying a polyolefin resin with an unsaturated carboxylic acid or a derivative thereof, or copolymerizing an acid functional group-containing monomer and an olefin. Especially, as (A) component, what was obtained by acid-modifying polyolefin resin is preferable.
Examples of the acid modification method include graft modification in which a polyolefin resin and an acid functional group-containing monomer are melt-kneaded in the presence of a radical polymerization initiator such as an organic peroxide or an aliphatic azo compound.
　前記ポリオレフィン系樹脂としては、ポリエチレン、ポリプロピレン、ポリ−１−ブテン、ポリイソブチレン、プロピレンとエチレン又はα−オレフィンとのランダム共重合体、プロピレンとエチレン又はα−オレフィンとのブロック共重合体等が挙げられる。なかでも、ホモポリプロピレン（プロピレン単独重合体；以下、「ホモＰＰ」ということがある。）、プロピレン−エチレンのブロック共重合体（以下、「ブロックＰＰ」ということがある。）、プロピレン−エチレンのランダム共重合体（以下、「ランダムＰＰ」ということがある）等のポリプロピレン系樹脂が好ましく、特にランダムＰＰが好ましい。
　共重合する場合の前記オレフィン類としては、エチレン、プロピレン、１−ブテン、イソブチレン、１−ヘキセン、α−オレフィン等のオレフィン系モノマーが挙げられる。 Examples of the polyolefin resin include polyethylene, polypropylene, poly-1-butene, polyisobutylene, a random copolymer of propylene and ethylene or α-olefin, and a block copolymer of propylene and ethylene or α-olefin. It is done. Among these, homopolypropylene (propylene homopolymer; hereinafter sometimes referred to as “homo PP”), propylene-ethylene block copolymer (hereinafter sometimes referred to as “block PP”), and propylene-ethylene. Polypropylene resins such as random copolymers (hereinafter sometimes referred to as “random PP”) are preferred, and random PP is particularly preferred.
Examples of the olefins for copolymerization include olefinic monomers such as ethylene, propylene, 1-butene, isobutylene, 1-hexene, and α-olefin.
　酸官能基含有モノマーは、エチレン性二重結合と、カルボキシ基又はカルボン酸無水物基とを同一分子内に有する化合物であって、各種の不飽和モノカルボン酸、ジカルボン酸、又はジカルボン酸の酸無水物が挙げられる。
　カルボキシ基を有する酸官能基含有モノマー（カルボキシ基含有モノマー）としては、アクリル酸、メタクリル酸、マレイン酸、ナジック酸、フマル酸、イタコン酸、シトラコン酸、クロトン酸、イソクロトン酸、テトラヒドロフタル酸、エンド−ビシクロ［２．２．１］−５−ヘプテン−２，３−ジカルボン酸（エンディック酸）などのα，β−不飽和カルボン酸モノマーが挙げられる。
　カルボン酸無水物基を有する酸官能基含有モノマー（カルボン酸無水物基含有モノマー）としては、無水マレイン酸、無水ナジック酸、無水イタコン酸、無水シトラコン酸、無水エンディック酸などの不飽和ジカルボン酸無水物モノマーが挙げられる。
　これらの酸官能基含有モノマーは、（Ａ）成分において１種類を単独で用いてもよく、２種類以上を併用してもよい。 The acid functional group-containing monomer is a compound having an ethylenic double bond and a carboxy group or a carboxylic anhydride group in the same molecule, and various unsaturated monocarboxylic acids, dicarboxylic acids, or dicarboxylic acid acids. Anhydrides are mentioned.
Acid functional group-containing monomers having carboxy groups (carboxy group-containing monomers) include acrylic acid, methacrylic acid, maleic acid, nadic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, tetrahydrophthalic acid, endo -Α, β-unsaturated carboxylic acid monomers such as bicyclo [2.2.1] -5-heptene-2,3-dicarboxylic acid (endic acid).
Examples of acid functional group-containing monomers having carboxylic anhydride groups (carboxylic anhydride group-containing monomers) include unsaturated dicarboxylic acids such as maleic anhydride, nadic anhydride, itaconic anhydride, citraconic anhydride, and endic anhydride An anhydride monomer is mentioned.
These acid functional group-containing monomers may be used alone or in combination of two or more in the component (A).
　なかでも酸官能基含有モノマーとしては、後述する（Ｂ）成分との反応性が高いことから、酸無水物基を有する酸官能基含有モノマーが好ましく、カルボン酸無水物基含有モノマーがより好ましく、無水マレイン酸が特に好ましい。
　酸変性に用いた酸官能基含有モノマーの一部が未反応である場合は、未反応の酸官能基含有モノマーによる接着力の低下を防ぐため、予め未反応の酸官能基含有モノマーを除去したものを（Ａ）成分として用いることが好ましい。 Among them, the acid functional group-containing monomer is preferably an acid functional group-containing monomer having an acid anhydride group, more preferably a carboxylic acid anhydride group-containing monomer, because of its high reactivity with the component (B) described later. Maleic anhydride is particularly preferred.
When a part of the acid functional group-containing monomer used for acid modification is unreacted, the unreacted acid functional group-containing monomer was removed in advance in order to prevent a decrease in adhesive strength due to the unreacted acid functional group-containing monomer. It is preferable to use those as the component (A).
　（Ａ）成分において、ポリオレフィン系樹脂又はオレフィン類由来の成分は、（Ａ）成分の全量１００質量部に対して、５０質量部以上であることが好ましい。 In the component (A), the component derived from the polyolefin resin or olefin is preferably 50 parts by mass or more with respect to 100 parts by mass of the total amount of the component (A).
　（Ａ）成分の融点は、（Ａ）成分と後述する（Ｂ）成分とを溶融混練する際の温度を考慮して、１００℃~１８０℃であることが好ましい。上記範囲の融点を有する（Ａ）成分を用いることにより、常法及び一般的な装置を用いた場合にも、（Ａ）成分と後述する（Ｂ）成分とを、（Ａ）成分の融点よりも十分に高い温度で溶融混練することができる。また、溶融混練を用いて（Ａ）成分と後述する（Ｂ）成分とを反応させる場合、（Ａ）成分に比して（Ｂ）成分の融点が低いことが好ましいが、上記範囲の融点を有する（Ａ）成分を用いることにより、（Ｂ）成分の選択の自由度を高めることができる。 The melting point of the component (A) is preferably 100 ° C. to 180 ° C. in consideration of the temperature when the component (A) and the component (B) described later are melt-kneaded. By using the component (A) having a melting point in the above range, the component (A) and the component (B) to be described later can be obtained from the melting point of the component (A) even when a conventional method and a general apparatus are used. Can be melt-kneaded at a sufficiently high temperature. In addition, when the component (A) is reacted with the component (B) described later using melt kneading, it is preferable that the melting point of the component (B) is lower than that of the component (A). By using the component (A), the degree of freedom in selecting the component (B) can be increased.
　また、上述のように（Ａ）成分の融点は、後述する（Ｂ）成分の融点よりも高いことが好ましいが、（Ａ）成分の融点は（Ｂ）成分の融点よりも１０℃以上高いことがより好ましく、２０℃以上高いことがさらに好ましく、３０℃以上高いことが特に好ましい。（Ａ）成分の融点が（Ｂ）成分よりも十分に高いことにより、溶融混練を行った際に（Ｂ）成分が先に溶融し、樹脂の形状を保持した状態の（Ａ）成分中に浸透し、（Ａ）成分と（Ｂ）成分とが均一に反応する結果、良好な耐久性を得ることができる。 Further, as described above, the melting point of the component (A) is preferably higher than the melting point of the component (B) described later, but the melting point of the component (A) is higher by 10 ° C. than the melting point of the component (B). More preferably, it is more preferably 20 ° C. or higher, and particularly preferably 30 ° C. or higher. When the melting point of the component (A) is sufficiently higher than that of the component (B), the component (B) is melted first when the melt kneading is performed, and the component (A) in the state where the shape of the resin is maintained. As a result of permeation and a uniform reaction between the component (A) and the component (B), good durability can be obtained.
　なかでも（Ａ）成分としては、接着性、及び適度な融点の観点から、無水マレイン酸変性ポリプロピレンが好ましい。 Among these, as the component (A), maleic anhydride-modified polypropylene is preferable from the viewpoints of adhesiveness and an appropriate melting point.
（フェノールノボラック型エポキシ樹脂（Ｂ））
　（Ｂ）成分は、常温で固体であるフェノールノボラック型エポキシ樹脂である。常温において固体である（Ｂ）成分を用いることで、溶融混練によって前記（Ａ）成分と（Ｂ）成分とを重合させる場合にも、（Ａ）成分の溶融温度に合わせて溶融混練を行うことができ、且つ、その際に（Ｂ）成分の特性が損なわれ難くなる。
　なお、本明細書中において「常温」とは、約３℃~約４０℃であり、好ましくは約１０℃~約３０℃であり、より好ましくは約１５℃~約２５℃であり、最も好ましくは約２３℃である。 (Phenol novolac type epoxy resin (B))
The component (B) is a phenol novolac type epoxy resin that is solid at room temperature. Even when the component (A) and the component (B) are polymerized by melt kneading by using the component (B) that is solid at normal temperature, melt kneading is performed in accordance with the melting temperature of the component (A). In that case, the characteristics of the component (B) are hardly impaired.
In the present specification, “normal temperature” is about 3 ° C. to about 40 ° C., preferably about 10 ° C. to about 30 ° C., more preferably about 15 ° C. to about 25 ° C., and most preferably. Is about 23 ° C.
　本発明においてフェノールノボラック型エポキシ樹脂（Ｂ）とは、フェノールとホルムアルデヒドとを酸縮合して得られるフェノールノボラック樹脂を基本構造とし、その構造の一部にエポキシ基が導入された化合物である。フェノールノボラック型エポキシ樹脂における１分子あたりのエポキシ基導入量は、特に限定されるものではないが、エピクロルヒドリン等のエポキシ基原料とフェノールノボラック樹脂とを反応させることにより、フェノールノボラック樹脂中に多数存在するフェノール性水酸基に多数のエポキシ基が導入されるため、通常は多官能エポキシ樹脂となる。 In the present invention, the phenol novolac type epoxy resin (B) is a compound in which a phenol novolac resin obtained by acid condensation of phenol and formaldehyde has a basic structure and an epoxy group is introduced into a part of the structure. The amount of epoxy group introduced per molecule in the phenol novolac type epoxy resin is not particularly limited, but there are many in the phenol novolac resin by reacting an epoxy group raw material such as epichlorohydrin with the phenol novolac resin. Since many epoxy groups are introduced into the phenolic hydroxyl group, it is usually a polyfunctional epoxy resin.
　なかでも（Ｂ）成分としては、基本骨格としてフェノールノボラック構造を有し、且つ、ビスフェノールＡ構造を併せて有する樹脂が好ましい。なお、（Ｂ）成分中のビスフェノールＡ構造は、ビスフェノールＡから誘導され得る構造であればよく、ビスフェノールＡの両端水酸基がエポキシ基含有基等の基で置換されていてもよい。
　（Ｂ）成分の一例としては、下記一般式（１）で表される樹脂が挙げられる。 Among these, the component (B) is preferably a resin having a phenol novolac structure as a basic skeleton and a bisphenol A structure. In addition, the bisphenol A structure in (B) component should just be a structure which can be induced | guided | derived from bisphenol A, and the both-ends hydroxyl group of bisphenol A may be substituted by groups, such as an epoxy group containing group.
(B) As an example of component, resin represented by the following general formula (1) is mentioned.
Figure JPOXMLDOC01-appb-I000001
［式（１）中、Ｒ１~Ｒ６は、それぞれ独立に水素原子又はメチル基であり、ｎは、０~１０の整数であり、ＲＸは、エポキシ基を有する基である。］
Figure JPOXMLDOC01-appb-I000001
[In Formula (1), R 1 to R 6 are each independently a hydrogen atom or a methyl group, n is an integer of 0 to 10, and R X is a group having an epoxy group. ]
　式（１）中、Ｒ１~Ｒ６は、それぞれ独立に水素原子又はメチル基である。ｎが２以上の整数の場合、Ｒ３、Ｒ４は、それぞれ同じであっても異なっていてもよい。
　式（１）で表される樹脂は、下記（ｉ）~（ｉｉｉ）の少なくともいずれか１つを満たすことが好ましい。
　（ｉ）Ｒ１及びＲ２の両方がメチル基
　（ｉｉ）Ｒ３及びＲ４の両方がメチル基
　（ｉｉｉ）Ｒ５及びＲ６の両方がメチル基
　例えば、上記（ｉ）を満たすことにより、式（１）においてＲ１及びＲ２が結合する炭素原子と、当該炭素原子が結合する２つのヒドロキシフェニル基とがビスフェノールＡから誘導される構造を構成することとなる。 In formula (1), R 1 to R 6 are each independently a hydrogen atom or a methyl group. When n is an integer of 2 or more, R 3 and R 4 may be the same or different.
The resin represented by the formula (1) preferably satisfies at least one of the following (i) to (iii).
(I) Both R 1 and R 2 are methyl groups (ii) Both R 3 and R 4 are methyl groups (iii) Both R 5 and R 6 are methyl groups For example, by satisfying the above (i), In the formula (1), the carbon atom to which R 1 and R 2 are bonded and the two hydroxyphenyl groups to which the carbon atom is bonded constitute a structure derived from bisphenol A.
　式（１）中、ＲＸはエポキシ基を有する基である。エポキシ基を有する基としては、エポキシ基、エポキシ基とアルキレン基との組み合わせ等が挙げられ、なかでもグリシジル基が好ましい。 In Formula (1), R X is a group having an epoxy group. Examples of the group having an epoxy group include an epoxy group, a combination of an epoxy group and an alkylene group, and among them, a glycidyl group is preferable.
　（Ｂ）成分のエポキシ当量は、１００~３００であることが好ましく、２００~３００であることがより好ましい。エポキシ当量（ｇ／ｅｑ）は、エポキシ基１個あたりのエポキシ樹脂の分子量であって、この値が小さいほど樹脂中のエポキシ基が多いことを意味する。エポキシ当量の比較的小さい（Ｂ）成分を用いることにより、（Ｂ）成分の添加量を比較的少量とした場合にも、（Ｂ）成分と被着体との接着性が良好となり、且つ、（Ｂ）成分と前記（Ａ）成分とが十分に架橋する。 The epoxy equivalent of the component (B) is preferably 100 to 300, and more preferably 200 to 300. The epoxy equivalent (g / eq) is the molecular weight of the epoxy resin per epoxy group, and the smaller the value, the more epoxy groups in the resin. By using the component (B) having a relatively small epoxy equivalent, the adhesion between the component (B) and the adherend becomes good even when the amount of the component (B) added is relatively small, and The component (B) and the component (A) are sufficiently crosslinked.
　このような（Ｂ）成分としては、三菱化学社製のｊＥＲ１５４、ｊＥＲ１５７Ｓ７０、ｊＥＲ−１５７Ｓ６５；ＤＩＣ社製のＥＰＩＣＬＯＮ　Ｎ−７３０Ａ、ＥＰＩＣＬＯＮ　Ｎ−７４０、ＥＰＩＣＬＯＮ　Ｎ−７７０、ＥＰＩＣＬＯＮＮ−７７５（以上、いずれも商品名）等の市販品を用いることもできる。 As such component (B), jER154, jER157S70, jER-157S65 manufactured by Mitsubishi Chemical Corporation; EPICLON N-730A, EPICLON N-740, EPICLON N-770, EPICLONN-775 (all above, manufactured by DIC) Commercial products such as (trade name) can also be used.
　本発明の接着性樹脂組成物は、（Ａ）成分の酸官能基と、（Ｂ）成分のエポキシ基との双方が、被着体（特に被着体が有する水酸基等の官能基）に対する接着性官能基として機能することにより、金属、ガラス、プラスチックなどの各種の被着体に対して、優れた接着性を奏することが可能となると考えられる。
　また、（Ａ）成分の酸官能基の一部と、（Ｂ）成分のエポキシ基の一部とが反応し、（Ａ）成分及び（Ｂ）成分の架橋構造ができ、この架橋構造により樹脂の強度が補強され、優れた接着性と共に良好な耐久性が得られるものと考えられる。 In the adhesive resin composition of the present invention, both the acid functional group of the component (A) and the epoxy group of the component (B) are bonded to an adherend (particularly a functional group such as a hydroxyl group possessed by the adherend). By functioning as a functional functional group, it is considered that excellent adhesion to various adherends such as metal, glass, and plastic can be achieved.
In addition, a part of the acid functional group of the component (A) and a part of the epoxy group of the component (B) react to form a crosslinked structure of the component (A) and the component (B). It is considered that the strength of the resin is reinforced and good durability is obtained together with excellent adhesiveness.
　本発明の接着性樹脂組成物において、（Ａ）成分９０~９９．９質量部に対して、（Ｂ）成分は０．１~１０質量部で含有される。さらに好ましくは（Ａ）成分９５~９９質量部に対して、（Ｂ）成分が１~５％質量部であり、最も好ましくは（Ａ）成分９７~９９質量部に対して、（Ｂ）成分が１~３％質量部である。
　本発明の接着剤組成物は、所望により混和性のある添加剤、付加的な樹脂、可塑剤、安定剤、着色剤等を適宜含有することができる。 In the adhesive resin composition of the present invention, the component (B) is contained in an amount of 0.1 to 10 parts by mass with respect to 90 to 99.9 parts by mass of the component (A). More preferably, the component (B) is 1 to 5% by mass with respect to 95 to 99 parts by mass of the component (A), and most preferably the component (B) with respect to 97 to 99 parts by mass of the component (A). Is 1 to 3% by mass.
The adhesive composition of the present invention can appropriately contain miscible additives, additional resins, plasticizers, stabilizers, colorants and the like as desired.
［接着剤の製造方法］
　本発明の第二の態様である接着剤の製造方法は、酸変性ポリオレフィン樹脂（Ａ）と、フェノールノボラック型エポキシ樹脂（Ｂ）とを溶融混練するものである。酸変性ポリオレフィン樹脂（Ａ）、フェノールノボラック型エポキシ樹脂（Ｂ）としてはそれぞれ、上述した第一の態様の（Ａ）成分、（Ｂ）成分と同様である。前記（Ａ）成分と、前記（Ｂ）成分とを含有する前記接着剤樹脂組成物を、公知の装置を用いて溶融混練することにより、（Ａ）成分と（Ｂ）成分とを反応させることができる。
　溶融混練の装置としては、一軸押出機、多軸押出機、バンバリーミキサー、プラストミル、加熱ロールニーダーなどを使用することができる。（Ａ）成分及び（Ｂ）成分の反応時における、（Ｂ）成分のエポキシ基の分解を抑制するため、水分等のエポキシ基と反応し得る揮発成分は、予め装置外へ除去しておき、且つ、反応中に揮発成分が発生する場合には脱気等により随時装置外へ排出することが望ましい。
　前記酸変性ポリオレフィン樹脂（Ａ）が、酸官能基として酸無水物基を有する場合、前記（Ｂ）成分のエポキシ基との反応性が高く、より穏和な条件下で反応が可能となるため好ましい。 [Method for producing adhesive]
The method for producing an adhesive according to the second aspect of the present invention melts and kneads an acid-modified polyolefin resin (A) and a phenol novolac epoxy resin (B). The acid-modified polyolefin resin (A) and the phenol novolac type epoxy resin (B) are the same as the component (A) and the component (B) in the first aspect described above, respectively. (A) component and (B) component are made to react by melt-kneading the said adhesive resin composition containing the said (A) component and the said (B) component using a well-known apparatus. Can do.
As an apparatus for melt kneading, a single screw extruder, a multi-screw extruder, a Banbury mixer, a plast mill, a heated roll kneader, or the like can be used. In order to suppress the decomposition of the epoxy group of the component (B) during the reaction of the component (A) and the component (B), the volatile component that can react with the epoxy group such as moisture is previously removed from the apparatus, In addition, when a volatile component is generated during the reaction, it is desirable to discharge it from the apparatus as needed by degassing or the like.
When the acid-modified polyolefin resin (A) has an acid anhydride group as an acid functional group, it is preferable because the reactivity with the epoxy group of the component (B) is high and the reaction can be performed under milder conditions. .
　溶融混練時の加熱温度は、（Ａ）成分及び（Ｂ）成分が十分に溶融し、且つ熱分解しないという点で、２４０~３００℃の範囲内から選択することが好ましい。
　なお、混練温度は、溶融混練装置から押し出された直後における、溶融状態の接着性樹脂組成物に、熱電対を接触させる等の方法によって測定することが可能である。 The heating temperature at the time of melt kneading is preferably selected from the range of 240 to 300 ° C. in that the components (A) and (B) are sufficiently melted and are not thermally decomposed.
The kneading temperature can be measured by a method such as bringing a thermocouple into contact with the molten adhesive resin composition immediately after being extruded from the melt kneader.
［接着剤］
　本発明の第三の態様である接着剤は、前記第一の態様の接着剤樹脂組成物を溶融混練して得られるものであって、溶融混練の方法は上述した第二の態様と同様である。本発明の接着剤は、（Ａ）成分と（Ｂ）成分とを含有する前記接着性樹脂組成物より得られるものであるため、金属、ガラス、プラスチック等の各種の被着体同士を、経時劣化及び環境劣化が抑制された状態で良好に接着させることができる。 [adhesive]
The adhesive according to the third aspect of the present invention is obtained by melt-kneading the adhesive resin composition according to the first aspect, and the melt-kneading method is the same as in the second aspect described above. is there. Since the adhesive of the present invention is obtained from the adhesive resin composition containing the component (A) and the component (B), various adherends such as metal, glass, plastic, etc. It can be satisfactorily bonded in a state in which deterioration and environmental deterioration are suppressed.
［接着性積層体］
　本発明の第四の態様の接着性積層体は、第１の接着層、基材層、及び第２の接着層をこの順に備えて、前記第１の接着層又は第２の接着層のいずれか一方又は両方が前記第三の態様の接着剤から形成される。
　また、本発明の第五の態様の接着性積層体は、第１の接着層、第１の中間層、基材層、第２の中間層、及び第２の接着層をこの順に備えた接着性積層体であって、前記第１の接着層又は第２の接着層のいずれか一方又は両方が、前記第三の態様の接着剤から形成される。
　第四及び第五の接着性積層体は、前記本発明の接着性樹脂組成物から形成され、フィルム、シート等の形状を有する積層体であって、接着性樹脂フィルム、接着性樹脂シート等として多用途に用いることができる。 [Adhesive laminate]
The adhesive laminate of the fourth aspect of the present invention comprises a first adhesive layer, a base material layer, and a second adhesive layer in this order, and the first adhesive layer or the second adhesive layer. Either or both are formed from the adhesive of the third aspect.
Moreover, the adhesive laminated body of the 5th aspect of this invention is the adhesion | attachment provided with the 1st contact bonding layer, the 1st intermediate | middle layer, the base material layer, the 2nd intermediate | middle layer, and the 2nd contact bonding layer in this order. It is an adhesive laminated body, Comprising: Either one or both of the said 1st contact bonding layer or a 2nd contact bonding layer is formed from the adhesive agent of the said 3rd aspect.
The fourth and fifth adhesive laminates are laminates formed from the adhesive resin composition of the present invention and having a shape such as a film, a sheet, etc., as an adhesive resin film, an adhesive resin sheet, etc. It can be used for many purposes.
　第四及び第五の態様における第１及び第２の接着層は、少なくともいずれか一方が前記第三の態様の接着剤から形成されるものであるが、両方が第三の態様の接着剤から形成されることが好ましい。 At least one of the first and second adhesive layers in the fourth and fifth aspects is formed from the adhesive of the third aspect, but both are from the adhesive of the third aspect. Preferably it is formed.
　第四及び第五の態様における基材層は、十分な機械強度を有するものであれば特に限定されず、例えば、ポリエチレンナフタレート（ＰＥＮ）、ポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート（ＰＢＴ）等のポリエステル樹脂；環状オレフィンポリマー（ＣＯＰ）、メチルペンテンポリマー（ＴＰＸ）等のポリオレフィンポリマー等からなる合成樹脂フィルム；金属層；ガラス板等を用いることができる。
　なかでも、線膨張係数が低く、当該接着性積層体を用いて金属等の被着体を接着した際にも層間剥離を起こしづらいことから、ＰＥＮ、ＣＯＰ又はＴＰＸが好ましく、ＣＯＰ又はＴＰＸが特に好ましい。
　線膨張係数の低い樹脂を用いることにより、積層体に熱がかかり、或いは冷却されたときに積層体の収縮が小さくなり、金属を含んだ積層体のひずみが小さくなる。
　また、基材層に、添加物として粒子状もしくは繊維状のフィラーを入れることができる。フィラーは耐熱性の高いフィラーであればよく、有機フィラー、無機フィラーが挙げられる。フィラーを入れることにより、ホットメルト接着性積層体の収縮力をさらに抑えることができ、ホットメルト接着性積層体自体の強度を上げることもできる。本発明においては、基材層の耐熱性、収縮性の観点から無機フィラーを添加することが好ましい。
　無機フィラーとしては、炭酸カルシウム、炭酸マグネシウム、炭酸バリウムなどの炭酸塩；硫酸カルシウム、硫酸マグネシウム、硫酸バリウムなどの硫酸塩；塩化ナトリウム、塩化カルシウム、塩化マグネシウムなどの塩化物；酸化アルミニウム、酸化カルシウム、酸化マグネシウム、酸化亜鉛、酸化チタン、シリカなどの酸化物；タルク、スメクタイト、マイカ、カオリナイトなどの鉱物；炭素繊維、炭素粒子等の炭素化合物；ガラスからなる微粒子が挙げられる。また、形状としては、球状、棒状、板状等が挙げられるが、板状の化合物が好ましい。 The base material layer in the fourth and fifth embodiments is not particularly limited as long as it has sufficient mechanical strength. For example, polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), etc. Polyester resins of: synthetic resin films made of polyolefin polymers such as cyclic olefin polymers (COP) and methylpentene polymers (TPX); metal layers; glass plates and the like.
Among them, PEN, COP or TPX is preferable, and COP or TPX is particularly preferable because the linear expansion coefficient is low and it is difficult to cause delamination even when an adherend such as a metal is adhered using the adhesive laminate. preferable.
By using a resin having a low linear expansion coefficient, when the laminate is heated or cooled, the shrinkage of the laminate is reduced, and the strain of the laminate containing metal is reduced.
In addition, a particulate or fibrous filler can be added as an additive to the base material layer. The filler should just be a filler with high heat resistance, and an organic filler and an inorganic filler are mentioned. By containing a filler, the shrinkage force of the hot melt adhesive laminate can be further suppressed, and the strength of the hot melt adhesive laminate itself can be increased. In the present invention, it is preferable to add an inorganic filler from the viewpoint of heat resistance and shrinkability of the base material layer.
As inorganic fillers, carbonates such as calcium carbonate, magnesium carbonate and barium carbonate; sulfates such as calcium sulfate, magnesium sulfate and barium sulfate; chlorides such as sodium chloride, calcium chloride and magnesium chloride; aluminum oxide, calcium oxide, Examples include oxides such as magnesium oxide, zinc oxide, titanium oxide, and silica; minerals such as talc, smectite, mica, and kaolinite; carbon compounds such as carbon fiber and carbon particles; and fine particles made of glass. Examples of the shape include a spherical shape, a rod shape, and a plate shape, and a plate-like compound is preferable.
　第五の態様における第１の中間層は、基材層及び第１の接着層に対する接着性を有する層である。また、第２の中間層は、基材層及び第２の接着層に対する接着性を有する層である。
　第１の中間層及び第２の中間層に求められる接着性とは、基材層及び接着層の積層体としての強度を保つための強度の事を指しており、接着性が高いと層間剥離が起きにくくなる。
　第１の中間層及び第２の中間層の形成材料は、第１の中間層及び第２の中間層が上述の接着性を有するものであれば特に限定されないが、基材層の形成材料に応じて適宜選択される。 The 1st intermediate | middle layer in a 5th aspect is a layer which has adhesiveness with respect to a base material layer and a 1st contact bonding layer. The second intermediate layer is a layer having adhesion to the base material layer and the second adhesive layer.
The adhesiveness required for the first intermediate layer and the second intermediate layer refers to the strength to maintain the strength as a laminate of the base material layer and the adhesive layer. Is less likely to occur.
The material for forming the first intermediate layer and the second intermediate layer is not particularly limited as long as the first intermediate layer and the second intermediate layer have the above-mentioned adhesiveness. It is selected as appropriate.
　基材層の形成材料が環状オレフィンポリマー（ＣＯＰ）である場合、第１の中間層及び第２の中間層の形成材料は、酸変性ポリプロピレン、メタロセン系ポリエチレン、及びメタロセン系ポリプロピレンからなる群から選択される少なくとも１種であることが好ましい。すなわち、第１の中間層及び第２の中間層の形成材料としては、ポリプロピレン、メタロセン系ポリエチレン、及びメタロセン系ポリプロピレンからなる群から選択される１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
　例えば、第１の中間層及び第２の中間層の形成材料が、酸変性ポリプロピレン、メタロセン系ポリエチレン、及びメタロセン系ポリプロピレンの３成分からなる場合、これら３成分の合計を１００質量部としたとき、酸変性ポリプロピレンの配合量が１０質量部~４０質量部、メタロセン系ポリエチレンの配合量が３０質量部~５０質量部、メタロセン系ポリプロピレンの配合量が３０質量部~４０質量部であることが好ましく、酸変性ポリプロピレンの配合量が２０質量部、メタロセン系ポリエチレンの配合量が５０質量部、メタロセン系ポリプロピレンの配合量が３０質量部であることが特に好ましい。前記中間層を用いて本発明の本発明の第五の態様、すなわち接着層／中間層／基材層／中間層／接着層の５層構成を構成する際は、溶融押出流涎により同時に製膜形成することが好ましい。 When the material for forming the base material layer is a cyclic olefin polymer (COP), the material for forming the first intermediate layer and the second intermediate layer is selected from the group consisting of acid-modified polypropylene, metallocene polyethylene, and metallocene polypropylene It is preferable that it is at least one kind. That is, as a material for forming the first intermediate layer and the second intermediate layer, one kind selected from the group consisting of polypropylene, metallocene polyethylene, and metallocene polypropylene may be used alone, or two or more kinds may be used. You may use it in combination.
For example, when the formation material of the first intermediate layer and the second intermediate layer is composed of three components of acid-modified polypropylene, metallocene-based polyethylene, and metallocene-based polypropylene, when the total of these three components is 100 parts by mass, The compounding amount of the acid-modified polypropylene is preferably 10 to 40 parts by mass, the compounding amount of the metallocene polyethylene is preferably 30 to 50 parts by mass, and the compounding amount of the metallocene polypropylene is preferably 30 to 40 parts by mass, It is particularly preferable that the blending amount of the acid-modified polypropylene is 20 parts by weight, the blending amount of the metallocene-based polyethylene is 50 parts by weight, and the blending amount of the metallocene-based polypropylene is 30 parts by weight. When the intermediate layer is used to form the fifth aspect of the present invention, that is, a five-layer structure of adhesive layer / intermediate layer / base material layer / intermediate layer / adhesive layer, film formation is simultaneously performed by melt extrusion flow. It is preferable to form.
　基材層の形成材料がメチルペンテンポリマー（ＴＰＸ）である場合、第１の中間層及び第２の中間層の形成材料は、メチルペンテンポリマー、ポリブテン系エラストマー、及びポリプロピレンからなる群から選択される少なくとも１種であることが好ましい。すなわち第１の中間層及び第２の中間層の形成材料としては、メチルペンテンポリマー、ポリブテン系エラストマー、及びポリプロピレンからなる群から選択される１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。なお、メチルペンテンポリマーとしては、酸変性メチルペンテンポリマーを用いてもよい。
　例えば、第１の中間層及び第２の中間層の形成材料が、メチルペンテンポリマー、酸変性メチルペンテンポリマー、ポリブテン系エラストマー、及びポリプロピレンの４成分からなる場合、これら４成分の合計を１００質量部としたとき、メチルペンテンポリマーの配合量が１０質量部~７０質量部、さらに好ましくは２０質量部~５０質量部、酸変性メチルペンテンポリマーの配合量が０質量部~５０質量部、さらに好ましくは０質量部超３０質量部以下、ポリブテン系エラストマーの配合量が５質量部~４０質量部、さらに好ましくは１０質量部~３０質量部、ポリプロピレンの配合量が５質量部~４０質量部であることが好ましい。前記中間層を用いて本発明の本発明の第五の態様、すなわち接着層／中間層／基材層／中間層／接着層の５層構成を構成する際は、溶融押出流涎により同時に製膜形成することが好ましい。 When the forming material of the base layer is methylpentene polymer (TPX), the forming material of the first intermediate layer and the second intermediate layer is selected from the group consisting of methylpentene polymer, polybutene-based elastomer, and polypropylene. It is preferable that there is at least one. That is, as a material for forming the first intermediate layer and the second intermediate layer, one kind selected from the group consisting of methylpentene polymer, polybutene elastomer, and polypropylene may be used alone, or two or more kinds may be combined. May be used. An acid-modified methylpentene polymer may be used as the methylpentene polymer.
For example, when the material for forming the first intermediate layer and the second intermediate layer is composed of four components of methylpentene polymer, acid-modified methylpentene polymer, polybutene-based elastomer, and polypropylene, the total of these four components is 100 parts by mass. The blending amount of the methylpentene polymer is 10 to 70 parts by weight, more preferably 20 to 50 parts by weight, and the blending amount of the acid-modified methylpentene polymer is 0 to 50 parts by weight, more preferably More than 0 parts by mass and 30 parts by mass or less, the blending amount of the polybutene elastomer is 5 to 40 parts by weight, more preferably 10 to 30 parts by weight, and the blending amount of polypropylene is 5 to 40 parts by weight. Is preferred. When the intermediate layer is used to form the fifth aspect of the present invention, that is, a five-layer structure of adhesive layer / intermediate layer / base material layer / intermediate layer / adhesive layer, film formation is simultaneously performed by melt extrusion flow. It is preferable to form.
　接着性積層体は、例えば、第１の接着層、基材層、及び第２の接着層、又は、第１の接着層、第１の中間層、基材層、第２の中間層、及び第２の接着層を、押出成形機を用いて共押出することにより製造してもよく；別途溶融成膜した第１の接着層及び第２の接着層を、基材層の両面に熱ラミネートして製造してもよく（第四の態様）；基材層の両面に、第１及び第２の中間層材料を溶液塗布した後に乾燥させて第１及び第２の中間層を形成し、その後、別途溶融成膜した第１の接着層及び第２の接着層を、形成された第１及び第２の中間層上に熱ラミネートすることにより製造してもよい（第五の態様）。 The adhesive laminate includes, for example, a first adhesive layer, a base material layer, and a second adhesive layer, or a first adhesive layer, a first intermediate layer, a base material layer, a second intermediate layer, and The second adhesive layer may be produced by coextrusion using an extruder; the first adhesive layer and the second adhesive layer separately melt-formed are thermally laminated on both sides of the base material layer. (Fourth embodiment); on both sides of the base material layer, the first and second intermediate layer materials are applied by solution and then dried to form the first and second intermediate layers; Then, you may manufacture by thermally laminating the 1st contact bonding layer and the 2nd contact bonding layer which carried out separate melt-deposition on the formed 1st and 2nd intermediate layer (5th mode).
　第五の態様において塗布により中間層を設ける場合、中間層はオレフィン系のポリマーを用いて中間層を設けることが好ましい。オレフィン系ポリマーはポリエチレン、ポリプロピレン、ポリブテンが好ましく、マレイン酸等のカルボン酸によって酸変性されていることが好ましい。 In the fifth aspect, when the intermediate layer is provided by coating, the intermediate layer is preferably provided using an olefin-based polymer. The olefin polymer is preferably polyethylene, polypropylene, or polybutene, and is preferably acid-modified with a carboxylic acid such as maleic acid.
　接着性積層体における各層の厚さとしては、第１及び第２の接着層は５~８０μｍが好ましく、さらに１０~５０μｍが好ましい。基材層は５０~３００μｍが好ましく、さらに６０~２００μｍが好ましい。また、第１の中間層及び第２の中間層は、共押出により製造する場合は５~２０μｍが好ましく、溶液塗布により製造する場合には０．５~５μｍが好ましい。 As the thickness of each layer in the adhesive laminate, the first and second adhesive layers are preferably 5 to 80 μm, more preferably 10 to 50 μm. The substrate layer is preferably 50 to 300 μm, more preferably 60 to 200 μm. The first intermediate layer and the second intermediate layer are preferably 5 to 20 μm when manufactured by coextrusion, and preferably 0.5 to 5 μm when manufactured by solution coating.
［積層体］
　本発明の第六の態様の積層体は、第１の金属層、前記第四又は第五の態様の接着性積層体、及び第２の金属層をこの順に備えたものである。接着性積層体中の接着層が、本発明の接着性樹脂組成物から形成されるものであるため、金属同士を接着した場合にも良好な接着性及び耐久性を得ることが可能となる。第六の積層体に用いる接着性積層体は、その両面が金属層と接することから、前記第１及び第２の接着層の両方が本発明の接着性樹脂組成物（接着剤）から形成されることが好ましい。
　本発明の積層体を用いて接着する被着体である第１の金属層及び第２の金属層は、一般に知られている金属板、金属平面板もしくは金属箔を用いることができる。これらに用いられる金属としては、例えば、鉄、銅、アルミニウム、鉛、亜鉛、チタン、クロムであってよく、合金であるステンレス等であってもよい。また、金属によるめっき、金属を含む塗料による塗布加工により表面加工処理された金属もしくは非金属を第１又は第２の金属層として用いてもよい。特に好ましくは、鉄、アルミニウム、チタン、ステンレス、表面加工処理された金属からなる金属平面板もしくは金属箔であり、これらを第１の金属層及び／又は第２の金属層として用いることにより、本発明の接着層が特に強固な接着力を発揮する。 [Laminate]
The laminated body of the 6th aspect of this invention is equipped with the 1st metal layer, the adhesive laminated body of the said 4th or 5th aspect, and the 2nd metal layer in this order. Since the adhesive layer in the adhesive laminate is formed from the adhesive resin composition of the present invention, good adhesion and durability can be obtained even when metals are bonded together. Since both surfaces of the adhesive laminate used for the sixth laminate are in contact with the metal layer, both the first and second adhesive layers are formed from the adhesive resin composition (adhesive) of the present invention. It is preferable.
As the first metal layer and the second metal layer which are adherends to be bonded using the laminate of the present invention, generally known metal plates, metal flat plates, or metal foils can be used. Examples of the metal used for these include iron, copper, aluminum, lead, zinc, titanium, and chromium, and may also be stainless steel that is an alloy. Moreover, you may use the metal or non-metal surface-treated by the metal plating and the coating process by the coating material containing a metal as a 1st or 2nd metal layer. Particularly preferably, it is a metal flat plate or metal foil made of iron, aluminum, titanium, stainless steel, surface-treated metal, and these can be used as the first metal layer and / or the second metal layer. The adhesive layer of the invention exhibits a particularly strong adhesive force.
　以下、実施例により本発明をさらに詳細に説明するが、本発明はこれらの例によって限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
［実施例１−１~１−５、比較例１−１~１−４］
（接着性樹脂フィルム）
　表１中に示す（Ａ）成分及び（Ｂ）成分を、２８０℃２分間溶融混練後、押出成形により所定の厚さのフィルム状に成形して接着シートを得た。 [Examples 1-1 to 1-5, Comparative Examples 1-1 to 1-4]
(Adhesive resin film)
The components (A) and (B) shown in Table 1 were melt-kneaded at 280 ° C. for 2 minutes, and then formed into a film having a predetermined thickness by extrusion to obtain an adhesive sheet.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表１中、各略号はそれぞれ以下の意味を有する。［　］内の数値は配合量（質量部）である。
　（Ａ）−１：無水マレイン酸変性ポリプロピレン（融点１４０℃）
　（Ａ）−２：ポリプロピレン重合体（融点１４０℃）
　（Ａ）−３：無水マレイン酸変性１−ブテン−ポリプロピレン共重合体（融点１５０℃、１−ブテン：ポリプロピレン＝５０：５０（質量比））
　（Ｂ）−１：「ｊＥＲ１５７Ｓ７０」（商品名、三菱化学社製）（ビスフェノールＡ構造を有するフェノールノボラック型エポキシ樹脂；粘度＝８０；エポキシ当量＝２１０）
　（Ｂ）−２：「ｊＥＲ１５４」（商品名、三菱化学社製）（フェノールノボラック型エポキシ樹脂；粘度＝８０；エポキシ当量＝１８０） In Table 1, each abbreviation has the following meaning. The numerical value in [] is a compounding amount (part by mass).
(A) -1: Maleic anhydride-modified polypropylene (melting point: 140 ° C.)
(A) -2: Polypropylene polymer (melting point 140 ° C.)
(A) -3: Maleic anhydride modified 1-butene-polypropylene copolymer (melting point 150 ° C., 1-butene: polypropylene = 50: 50 (mass ratio))
(B) -1: “jER157S70” (trade name, manufactured by Mitsubishi Chemical Corporation) (phenol novolac type epoxy resin having a bisphenol A structure; viscosity = 80; epoxy equivalent = 210)
(B) -2: “jER154” (trade name, manufactured by Mitsubishi Chemical Corporation) (phenol novolac type epoxy resin; viscosity = 80; epoxy equivalent = 180)
（接着性評価）
　厚さ３００μｍ、縦１０ｍｍ×横３０ｍｍのアルミニウム箔、厚さ３００μｍ、縦１０ｍｍ×横３０ｍｍのステンレス箔、及び、上記で得られた各例の接着シートを１０ｍｍ×１０ｍｍに切出した接着シート片を用意した。
　アルミニウム箔の短辺端部に、接着シート片の一端が揃うように重ねた後、さらに、接着シート片の他端にステンレス箔の短辺端部が揃い、且つ、接着シート片を介してアルミニウム箔とステンレス箔とが重なり合うように載置した。０．５ＭＰａの圧力をかけながら、１５０℃で５秒間貼り合わせることで、接着面積１００ｍ３、平面視で縦１０ｍｍ×横５０ｍｍの大きさの積層体とした。
　得られた各例の積層体のアルミニウム箔、ステンレス箔の端部をそれぞれ治具によりはさみ、速度＝１０ｍｍ／分、チャック間距離＝２０ｍｍの条件で、引張せん断試験機を用いて引張せん断試験を行った。
　下記評価基準に基づいて評価を行った。結果を「接着性」として表１中に併記する。
　Ａ：せん断力が３２０Ｎ以上であった。
　Ｂ：せん断力が２５０Ｎ以上３２０Ｎ未満であった。
　Ｃ：せん断力が２００Ｎ以上２５０Ｎ未満であった。
　Ｄ：せん断力が２００Ｎ未満であった。 (Adhesion evaluation)
Prepare 300 mm thick, 10 mm long x 30 mm wide aluminum foil, 300 μm thick, 10 mm long x 30 mm wide stainless steel foil, and 10 mm x 10 mm adhesive sheet pieces obtained by cutting each of the above obtained adhesive sheets. did.
After overlapping the short side edge part of the aluminum foil so that one end of the adhesive sheet piece is aligned, the short side edge part of the stainless steel foil is aligned to the other end of the adhesive sheet piece, and the aluminum is interposed via the adhesive sheet piece. It mounted so that foil and stainless steel foil might overlap. While applying a pressure of 0.5 MPa, the laminate was bonded at 150 ° C. for 5 seconds to obtain a laminate having an adhesion area of 100 m 3 and a size of 10 mm in length and 50 mm in width in plan view.
The ends of the aluminum foil and stainless steel foil of each of the obtained laminates were sandwiched with jigs, and a tensile shear test was performed using a tensile shear tester under the conditions of speed = 10 mm / min and distance between chucks = 20 mm. went.
Evaluation was performed based on the following evaluation criteria. The results are also shown in Table 1 as “adhesiveness”.
A: The shearing force was 320 N or more.
B: Shear force was 250N or more and less than 320N.
C: Shear force was 200N or more and less than 250N.
D: Shear force was less than 200N.
（耐久性評価）
　上記接着性評価と同様にして得られた各例の積層体を、９５℃のお湯に１００時間漬けて耐久試験を行った。耐久試験後の試験サンプルである積層体のアルミニウム箔、ステンレス箔の端部をそれぞれ治具によりはさみ、速度＝１０ｍｍ／分、チャック間距離＝２０ｍｍの条件で、引張せん断試験機を用いて引張せん断試験を行った。
　下記評価基準に基づいて評価を行った。結果を「耐久性」として表１中に併記する。
　Ａ：せん断力が２５０Ｎ以上であった。
　Ｂ：せん断力が２００Ｎ以上２５０Ｎ未満であった。
　Ｃ：せん断力が１００Ｎ以上２００Ｎ未満であった。
　Ｄ：せん断力が１００Ｎ未満であった。 (Durability evaluation)
The laminated body of each example obtained similarly to the said adhesive evaluation was immersed in 95 degreeC hot water for 100 hours, and the durability test was done. The end of the aluminum foil and stainless steel foil of the laminate, which is a test sample after the durability test, was sandwiched between jigs, respectively, and tensile shear using a tensile shear tester under conditions of speed = 10 mm / min and chuck distance = 20 mm. A test was conducted.
Evaluation was performed based on the following evaluation criteria. The results are also shown in Table 1 as “durability”.
A: The shearing force was 250 N or more.
B: Shear force was 200N or more and less than 250N.
C: Shear force was 100N or more and less than 200N.
D: Shear force was less than 100N.
　表１に示す結果から、本発明の接着性樹脂組成物を用いた実施例１−１~１−５は、比較例１−１~１−４に比して優れた耐久性を有することが確認できた。 From the results shown in Table 1, Examples 1-1 to 1-5 using the adhesive resin composition of the present invention have superior durability compared to Comparative Examples 1-1 to 1-4. It could be confirmed.
［実施例２−１~２−４］
（接着性評価）
　前記（Ａ）−１の９８質量部と、前記（Ｂ）−１の２質量部とを、表２に示す温度で２分間溶融混練後、押出成形により所定の厚さのフィルム状に成形して接着シートを得た。
　得られた接着シートを用いて、上記接着性評価と同様にして積層体を作製し、上記同様に引張せん断試験を行った。
　上記評価基準と同様に評価を行った結果を表２中に併記する。 [Examples 2-1 to 2-4]
(Adhesion evaluation)
98 parts by mass of (A) -1 and 2 parts by mass of (B) -1 were melt-kneaded for 2 minutes at the temperatures shown in Table 2, and then formed into a film having a predetermined thickness by extrusion. To obtain an adhesive sheet.
Using the obtained adhesive sheet, a laminate was produced in the same manner as in the above-described adhesion evaluation, and a tensile shear test was conducted in the same manner as described above.
The results of evaluation similar to the above evaluation criteria are also shown in Table 2.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表２に示す結果から、本発明の接着性樹脂組成物を用いて、溶融混練を２４０~３００℃で行った場合、特に優れた接着性を有することが確認できた。 From the results shown in Table 2, it was confirmed that when the kneading was performed at 240 to 300 ° C. using the adhesive resin composition of the present invention, it had particularly excellent adhesiveness.
［実施例３−１~３−５］
　実施例３−１~３−５では、前記（Ａ）−１の９８質量部と、前記（Ｂ）−１の２質量部とを有する接着性樹脂組成物を用いた。 [Examples 3-1 to 3-5]
In Examples 3-1 to 3-5, an adhesive resin composition having 98 parts by mass of (A) -1 and 2 parts by mass of (B) -1 was used.
（実施例３−１）
　（Ａ）成分及び（Ｂ）成分を有する接着剤組成物を、２８０℃で２分間溶融混練後、ＰＥＮと共に共押出成形を行い、「接着層（厚さ４２μｍ）−ＰＥＮ基材（厚さ７５μｍ）−接着層（厚さ４２μｍ）」の３層構成からなる接着性積層体を得た。 (Example 3-1)
The adhesive composition having the component (A) and the component (B) was melt-kneaded at 280 ° C. for 2 minutes, and then co-extruded with PEN. “Adhesion layer (thickness 42 μm) -PEN substrate (thickness 75 μm) ) -Adhesive layer (thickness 42 μm) ”was obtained.
（実施例３−２）
　厚さ７５μｍのＰＥＮ基材の両面に、厚さ２．０μｍの中間層を形成するように、マレイン酸変性プロピレン−ブテン共重合体の分散溶液を溶液塗布し、乾燥させた。
　また、（Ａ）成分及び（Ｂ）成分を有する接着剤組成物を、２８０℃で２分間溶融混練後、押出成形して接着フィルム（厚さ４０μｍ）を２枚製造した。
　次いで、ＰＥＮ基材の両面に設けられた中間層上に、別途得られた上記接着フィルムを載置して１７０℃で熱ラミネートし、「接着層−中間層−ＰＥＮ基材−中間層−接着層」の５層構成からなる接着性積層体を得た。 (Example 3-2)
A dispersion solution of a maleic acid-modified propylene-butene copolymer was applied on both sides of a PEN substrate having a thickness of 75 μm so as to form an intermediate layer having a thickness of 2.0 μm, and dried.
Moreover, the adhesive composition having the component (A) and the component (B) was melt-kneaded at 280 ° C. for 2 minutes and then extruded to produce two adhesive films (thickness 40 μm).
Next, the adhesive film obtained separately was placed on the intermediate layer provided on both sides of the PEN base material and heat laminated at 170 ° C., and “adhesive layer-intermediate layer-PEN base material-intermediate layer-adhesion” was obtained. An adhesive laminate having a five-layer structure of “layer” was obtained.
（実施例３−３）
　（Ａ）成分及び（Ｂ）成分を有する接着剤組成物を、２８０℃で２分間溶融混練後、基材となるＣＯＰ、中間層となる、ポリプロピレンとメタロセン系ポリエチレンとメタロセン系ポリプロピレンとスチレン系熱可塑性エラストマーとの混合ポリマーと共に共押出成形を行い、「接着層（厚さ２７μｍ）−中間層（厚さ１５μｍ）−ＣＯＰ基材（厚さ７５μｍ）−中間層（厚さ１５μｍ）−接着層（厚さ２７μｍ）」の５層構成からなる接着性積層体を得た。 (Example 3-3)
After melt-kneading the adhesive composition having the component (A) and the component (B) at 280 ° C. for 2 minutes, COP as the base material, and intermediate layer, polypropylene, metallocene polyethylene, metallocene polypropylene, and styrene heat Co-extrusion is performed together with a polymer blended with a plastic elastomer, and “adhesion layer (thickness 27 μm) —intermediate layer (thickness 15 μm) —COP substrate (thickness 75 μm) —intermediate layer (thickness 15 μm) —adhesion layer ( An adhesive laminate having a five-layer structure having a thickness of 27 μm) ”was obtained.
（実施例３−４）
　（Ａ）成分及び（Ｂ）成分を有する接着剤組成物を、２８０℃で２分間溶融混練後、基材となるＴＰＸ、中間層となる、メチルペンテンポリマーとポリブテンとポリプロピレンとの混合ポリマーと共に共押出成形を行い、「接着層（厚さ２７μｍ）−中間層（厚さ１５μｍ）−ＴＰＸ基材（厚さ７５μｍ）−中間層（厚さ１５μｍ）−接着層（厚さ２７μｍ）」の５層構成からなる接着性積層体を得た。 (Example 3-4)
After melt-kneading the adhesive composition having the component (A) and the component (B) at 280 ° C. for 2 minutes, the TPX as the base material and the mixed polymer of methylpentene polymer, polybutene and polypropylene as the intermediate layer are used together. Extrusion molding was performed, and five layers of “adhesive layer (thickness 27 μm) —intermediate layer (thickness 15 μm) —TPX substrate (thickness 75 μm) —intermediate layer (thickness 15 μm) —adhesive layer (thickness 27 μm)” An adhesive laminate having the structure was obtained.
（実施例３−５）
　（Ａ）成分及び（Ｂ）成分を有する接着剤組成物を、２８０℃で２分間溶融混練後、押出成形して接着フィルム（厚さ１５９μｍ）を製造した。 (Example 3-5)
The adhesive composition having the component (A) and the component (B) was melt-kneaded at 280 ° C. for 2 minutes and then extruded to produce an adhesive film (thickness: 159 μm).
（積層体の耐久強度評価）
　厚さ３００μｍ、縦３０ｍｍ×横３０ｍｍのアルミニウム箔に、各例の３層若しくは５層接着性積層体又は接着フィルムを３０ｍｍ×３０ｍｍに切り出したものを積層し、その上に厚さ３００μｍ、縦３０ｍｍ×横３０ｍｍに切り出したステンレス箔の端部を載置して、０．５ＭＰａの圧力をかけながら、１５０℃で５秒間貼り合わせて積層体とした。
　この積層体を９５℃のお湯に３００時間漬け、浸漬後の積層体の状態を観察して評価を行った。結果を「積層体強度」として表３に示す。
　Ａ：目に見える剥がれがなく、積層体のゆがみも見られなかった。
　Ｂ：目に見えて目立った、剥がれが見られず、大きなゆがみも見られなかった。
　Ｃ：若干の剥がれ、もしくは若干の積層体のゆがみが見られたが、許容範囲内であった。
　Ｄ：全面に剥がれが見られ、積層体がゆがんでいた。 (Evaluation of durability of laminates)
The aluminum foil having a thickness of 300 μm and a length of 30 mm × width of 30 mm is laminated with a three-layer or five-layer adhesive laminate or an adhesive film of each example cut into 30 mm × 30 mm, and the thickness is 300 μm and length is 30 mm. X The end of the stainless steel foil cut out to 30 mm in width was placed, and the laminate was laminated at 150 ° C. for 5 seconds while applying a pressure of 0.5 MPa.
The laminate was immersed in 95 ° C. hot water for 300 hours, and the state of the laminate after immersion was observed and evaluated. The results are shown in Table 3 as “laminate strength”.
A: There was no visible peeling, and no distortion of the laminate was observed.
B: Visible and conspicuous, no peeling was seen, and no major distortion was seen.
C: Some peeling or some distortion of the laminate was observed, but it was within the allowable range.
D: Peeling was observed on the entire surface, and the laminate was distorted.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表３に示す結果から、本発明の接着性樹脂組成物を用いて、接着層と基材シートとの間に中間層を設ける構成とした場合、特に優れた積層体強度を有することが確認できた。また、接着した積層体の接着性・耐久性はいずれも良好であった。 From the results shown in Table 3, it can be confirmed that when the adhesive resin composition of the present invention is used and an intermediate layer is provided between the adhesive layer and the base sheet, it has particularly excellent laminate strength. It was. Moreover, both the adhesiveness and durability of the laminated body adhered were good.

Claims (11)

  1. 　酸変性ポリオレフィン樹脂（Ａ）９０~９９．９質量部と、
    　常温で固体であるフェノールノボラック型エポキシ樹脂（Ｂ）０．１~１０質量部と、
    を含有することを特徴とする接着性樹脂組成物。     90 to 99.9 parts by mass of acid-modified polyolefin resin (A),
    0.1 to 10 parts by mass of a phenol novolac type epoxy resin (B) that is solid at room temperature;
    An adhesive resin composition comprising:
  2. 　前記酸変性ポリオレフィン樹脂（Ａ）９５~９９．９質量部と、
    　前記フェノールノボラック型エポキシ樹脂（Ｂ）０．１~５質量部と、
    を含有する、請求項１記載の接着性樹脂組成物。     95 to 99.9 parts by mass of the acid-modified polyolefin resin (A),
    0.1 to 5 parts by mass of the phenol novolac type epoxy resin (B),
    The adhesive resin composition according to claim 1, comprising:
  3. 　前記フェノールノボラック型エポキシ樹脂（Ｂ）が、ビスフェノールＡ構造を有する、請求項１又は２に記載の接着性樹脂組成物。 The adhesive resin composition according to claim 1 or 2, wherein the phenol novolac epoxy resin (B) has a bisphenol A structure.
  4. 　前記フェノールノボラック型エポキシ樹脂（Ｂ）のエポキシ当量が、１００~３００である、請求項１~３のいずれか一項に記載の接着性樹脂組成物。 The adhesive resin composition according to any one of claims 1 to 3, wherein an epoxy equivalent of the phenol novolac type epoxy resin (B) is 100 to 300.
  5. 　前記酸変性ポリオレフィン樹脂（Ａ）は、融点が１００~１８０℃の無水マレイン酸変性ポリプロピレンであって、
    　前記酸変性ポリオレフィン樹脂（Ａ）の融点が、前記フェノールノボラック型エポキシ樹脂（Ｂ）の融点よりも高い、請求項１~４のいずれか一項に記載の接着性樹脂組成物。     The acid-modified polyolefin resin (A) is a maleic anhydride-modified polypropylene having a melting point of 100 to 180 ° C.,
    The adhesive resin composition according to any one of claims 1 to 4, wherein the acid-modified polyolefin resin (A) has a melting point higher than that of the phenol novolac epoxy resin (B).
  6. 　請求項１~５のいずれか一項に記載の接着性樹脂組成物を用いて接着剤を製造する方法であって、
    　前記酸変性ポリオレフィン樹脂（Ａ）と、前記フェノールノボラック型エポキシ樹脂（Ｂ）とを溶融混練することを特徴とする、接着剤の製造方法。     A method for producing an adhesive using the adhesive resin composition according to any one of claims 1 to 5,
    A method for producing an adhesive, comprising melt-kneading the acid-modified polyolefin resin (A) and the phenol novolac epoxy resin (B).
  7. 　前記溶融混練が２４０~３００℃の加熱下で行われる、請求項６に記載の接着剤の製造方法。 The method for producing an adhesive according to claim 6, wherein the melt-kneading is performed under heating at 240 to 300 ° C.
  8. 　請求項１~５のいずれか一項に記載の接着性樹脂組成物を溶融混練して得られることを特徴とする接着剤。 An adhesive obtained by melt-kneading the adhesive resin composition according to any one of claims 1 to 5.
  9. 　第１の接着層、基材層、及び第２の接着層をこの順に備えた接着性積層体であって、
    　前記第１の接着層又は第２の接着層のいずれか一方又は両方が、請求項８に記載の接着剤から形成されることを特徴とする接着性積層体。     An adhesive laminate comprising a first adhesive layer, a base material layer, and a second adhesive layer in this order,
    Either one or both of said 1st contact bonding layer or 2nd contact bonding layer is formed from the adhesive agent of Claim 8, The adhesive laminated body characterized by the above-mentioned.
  10. 　第１の接着層、第１の中間層、基材層、第２の中間層、及び第２の接着層をこの順に備えた接着性積層体であって、
    　前記第１の接着層又は第２の接着層のいずれか一方又は両方が、請求項８に記載の接着剤から形成されることを特徴とする接着性積層体。     An adhesive laminate comprising a first adhesive layer, a first intermediate layer, a base material layer, a second intermediate layer, and a second adhesive layer in this order,
    Either one or both of said 1st contact bonding layer or 2nd contact bonding layer is formed from the adhesive agent of Claim 8, The adhesive laminated body characterized by the above-mentioned.
  11. 　第１の金属層、請求項９又は１０に記載の接着性積層体、及び第２の金属層をこの順に備えたことを特徴とする積層体。 A laminate comprising the first metal layer, the adhesive laminate according to claim 9 or 10, and the second metal layer in this order.
PCT/IB2016/001085 2015-08-06 2016-08-02 Adhesive resin composition, production method for adhesive, adhesive, adhesive laminate, and laminate WO2017037524A1 (en)

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