JP6263806B2 - Adhesive resin film and adhesive resin laminate - Google Patents

Description

The present invention relates to an adhesive resin film having an excellent adhesive force to various adherends such as metal, glass, and plastic, and an adhesive resin laminate.

  Conventionally, as a protective film for covering and protecting the surface of various metal plates, such as a steel plate, an aluminum plate, or a metal plate subjected to various surface treatments such as plating on the metal plate, for example, a laminate with a metal Films are known (Patent Document 1). Further, an interlayer film for laminated glass is known as an adhesive resin for a glass plate (Patent Document 2).

Patent Document 1 discloses a laminated film for metal laminate comprising an adhesive layer made of an unsaturated carboxylic acid-modified polypropylene resin and one or more drawn polypropylene resin layers.
However, in Patent Document 1, as a heat seal condition with a metal material, the temperature on the metal material side is set to 220 ° C. and the temperature on the film side is set to 90 ° C. in a heat sealer. Thus, in the prior art, even if thermocompression bonding is performed at a high temperature, an excellent adhesive force is not obtained. For this reason, there existed a problem that the improvement for further improving adhesive force was required.

Patent Document 2 discloses an interlayer film for laminated glass containing an ethylene-vinyl acetate copolymer, an acid-modified polyolefin, and inorganic fine particles. In particular, when the acid value of the acid-modified polyolefin is 10 mgKOH / g or more and 0.01 to 5 parts by weight of the acid-modified polyolefin is contained with respect to 100 parts by weight of the ethylene-vinyl acetate copolymer, excellent adhesiveness is obtained. You can get.
However, the resin composition disclosed in Patent Document 2 has a problem that when the content of the acid-modified polyolefin exceeds 5 parts by weight, sufficient adhesion between the interlayer film for laminated glass and the glass plate cannot be obtained. It was.

JP 2002-192672 A JP 2009-184887 A

  In the prior art, an adhesive composition that has an excellent adhesive force to various adherends such as metal, glass, and plastic, has a simple composition, and can be easily manufactured is known. It wasn't.

In view of the above circumstances, metal, glass, to various adherends such as plastic, has excellent adhesive power and a simple composition, easy to manufacture adhesive resin film And an adhesive resin laminate.

In order to solve the above problems, the present invention has an acid-modified polyolefin resin (A) from which unreacted acid functional group-containing monomers have been removed , two or more epoxy groups in one molecule, and the unreacted a functional group acid functional group-containing monomer is reacted with the acid functionality of the acid-modified polyolefin resin that has been removed (a), epoxy resin-based compound having 5 or more in one molecule and (B), as essential components An adhesive resin film formed from an adhesive resin composition that does not contain a radical generator , wherein the adhesive resin composition is an acid-modified polyolefin from which the unreacted acid functional group-containing monomer has been removed. Resin (A) acid functional group and the functional group which the said epoxy resin type compound (B) has contain the graft copolymer (G) obtained by graft polymerization, The said unreacted acid functionality Group-containing products Over acid-modified polyolefin resin that has been removed (A) is, unreacted acid functional group-containing monomer is acid-modified polypropylene-based resin has been removed, or unreacted acid functional group-containing monomer is acid-modified polyethylene resin which is removed , and the heat sealing temperature of the adhesive resin film, to provide an adhesive resin film, which is a 140 ° C. to 180 ° C..
It is preferable that the functional group which the said epoxy resin type compound (B) has is only an epoxy group and a hydroxyl group, or an epoxy group.
The epoxy resin compound (B) is preferably contained in the range of 1 to 15 parts by weight in 100 parts by weight of the solid content of the adhesive resin composition.
The acid-modified polyolefin resin (A) is preferably an acid-modified polypropylene resin or an acid-modified polyethylene resin.
It is preferable to further add so that the thermoplastic elastomer resin (C) is contained in the range of 1 to 15 parts by weight in 100 parts by weight of the solid content of the adhesive resin composition.
Moreover, this invention provides the adhesive resin laminated body by which the said adhesive resin film is laminated | stacked on the at least single side | surface of a base material.

According to the present invention, metal, glass, to various adherends such as plastic, has excellent adhesive power and a simple composition, readily manufacturable adhesive resin film, and adhesion It becomes possible to provide a conductive resin laminate.

Hereinafter, the present invention will be described based on preferred embodiments.
The adhesive resin composition of the present invention has an acid-modified polyolefin resin (A), a functional group having two or more epoxy groups in one molecule and reacting with the acid functional group of the acid-modified polyolefin resin (A). An epoxy resin compound (B) having 5 or more groups per molecule is an essential component.

[Acid-modified polyolefin resin (A)]
The acid-modified polyolefin resin (A) used in the present invention is a polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof, and has a carboxyl group or a carboxylic anhydride group in the polyolefin resin. Preferably, a polyolefin resin is modified with an unsaturated carboxylic acid or a derivative thereof. Acid modification methods for acid-modified polyolefin resins include graft modification such as melt-kneading an acid functional group-containing monomer with a polyolefin resin in the presence of a radical polymerization initiator such as an organic peroxide or an aliphatic azo compound, Examples thereof include copolymerization of a group-containing monomer and olefins.

Examples of the polyolefins 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. . Among these, polypropylene resins such as homopolypropylene (homo PP, propylene homopolymer), propylene-ethylene block copolymer (block PP), and propylene-ethylene random copolymer (random PP) are preferable. In particular, random PP is preferable.
Examples of the olefins for copolymerization include olefinic monomers such as ethylene, propylene, 1-butene, isobutylene, 1-hexene, and α-olefin.

The acid functional group-containing monomer is a compound having an ethylenic double bond and a carboxylic acid group or carboxylic anhydride group in the same molecule, and various unsaturated monocarboxylic acids, dicarboxylic acids, or dicarboxylic acids. Consisting of acid anhydride.
Examples of the acid functional group-containing monomer having a carboxylic acid group (carboxylic acid group-containing monomer) include acrylic acid, methacrylic acid, maleic acid, nadic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, tetrahydrophthalic acid And α, β-unsaturated carboxylic acid monomers such as endo-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 acid-modified polyolefin resin (A).

Of the acid functional group-containing monomers, more preferred are carboxylic anhydride group-containing monomers, and more preferred is maleic anhydride.
When a part of the acid functional group-containing monomer used for acid modification is unreacted, the acid-modified polyolefin resin is prepared by removing the unreacted acid functional group-containing monomer in order to suppress adverse effects on adhesive strength. It is preferable to use as (A).

  Regarding the propylene component in the acid-modified polyolefin resin (A), it is preferable that the propylene unit is a majority amount from the viewpoint of heat resistance of the resin. A majority amount here means that the propylene component with respect to acid-modified polyolefin resin (A) is 50 weight% or more. Accordingly, the acid-modified polyolefin resin (A) is preferably an acid-modified polypropylene resin having a majority of propylene units.

[Epoxy resin compound (B)]
The epoxy resin compound (B) used in the present invention has two or more epoxy groups in one molecule, and one functional group that reacts with the acid functional group of the acid-modified polyolefin resin (A). It is a compound having 5 or more in it.
As the epoxy resin compound (B), in one molecule by epoxidation such as glycidylation on a polymer having a large number of hydroxyl groups such as polyhydroxy polyether, polyhydroxy polyester, polyhydroxy polycarbonate, polyhydroxy polyamide, etc. Examples thereof include compounds having two or more epoxy groups. Specific examples thereof include an epoxy resin-based compound represented by the following general formula (1), which is a phenoxy resin synthesized by reacting a bisphenol and epichlorohydrin and having an epoxy group at both ends. It is done.

In the general formula (1), examples of the substituents R and R ′ each independently include a hydrogen atom or an alkyl group such as a methyl group or an ethyl group. The integer p is equal to the number of hydroxyl groups (number of hydroxyl groups) in one molecule. In this case, the functional group that reacts with the acid functional group of the acid-modified polyolefin resin (A) is p hydroxyl groups and two epoxy groups at both ends. In order to have 5 or more functional groups that react with the acid functional group in one molecule, it is preferable that p + 2 ≧ 5.
Examples of the phenoxy resin include bisphenol A (BPA) type phenoxy resin in which the substituents R and R ′ of the bisphenols in the general formula (1) are both CH ₃ , and bisphenol F (BPF) in which both R and R ′ are H. ) Type phenoxy resin, bisphenol A type and bisphenol F type copolymerized BPA / BPF copolymer type phenoxy resin, one of R and R 'is CH ₃ and the other is H And phenoxy resin. Since the bisphenol-type epoxy resin is represented by the above general formula (1) like the phenoxy resin, it can be selected and used having a relatively high molecular weight and a large number of hydroxyl groups p.

The weight average molecular weight (Mw) of the phenoxy resin or epoxy resin is preferably about 3,000 (in the case of bisphenol A type, the number of hydroxyl groups p is about 10) or more, and about 15,000 (in the case of bisphenol A type, the number of hydroxyl groups). p is about 50), about 20,000 (in the case of the bisphenol A type, the number of hydroxyl groups p is about 70), and those having a higher molecular weight can also be used.
The upper limit of the average molecular weight of the phenoxy resin or epoxy resin is not particularly limited, but is preferably about 80,000 (in the case of bisphenol A type, the number of hydroxyl groups p is about 280). In addition, when calculating | requiring the average molecular weight of a phenoxy resin or an epoxy resin by GPC, tetrahydrofuran (THF) is used as an eluent of GPC, for example, TSKgel G4000H and TSKgel G3000H (both manufactured by Tosoh Corporation, Product name) can be used.

As such phenoxy resin, trade name: YP-50 (Mw is 60,000 to 80,000, BPA type, hydroxyl group number p is about 210 to 280) manufactured by Nippon Steel Chemical Co., Ltd., YP-50S ( Mw is 50,000 to 70,000, BPA type, hydroxyl number p is about 175 to 245), YP-55U (Mw is 40,000 to 45,000, BPA type, hydroxyl number p is about 140 to 160), YP-70 (Mw is 50,000-60,000, BPA / BPF copolymer type), ZX-1356-2 (Mw is 60,000-80,000, BPA / BPF copolymer type), FX-316 ( Mw is 40,000-60,000, BPF type) and the like; Phenoxy type grade 1256 (molecular weight of about 50000, BPA type) manufactured by Mitsubishi Chemical Corporation, 4250 (molecular weight of about 60000, PA / BPF copolymer type), the 4275 (molecular weight of about 60000, BPA / BPF copolymer type), 1255HX30, YX8100BH30, YX6954BH30 like; Tomoe Co., Ltd. PKHB, PKHC, PKHH, PKHJ, and the like.
Moreover, as an epoxy resin, Nippon Steel Chemical Co., Ltd. brand name: YD-020G (epoxy equivalent 3500-4500, BPA type) etc .; Mitsubishi Chemical Corporation grade 1010 (average molecular weight 5500, BPA type, epoxy) Equivalent 3000 to 5000), 1009 (average molecular weight 3800, BPA type, epoxy equivalent 2400 to 3300) and the like.

  Moreover, as an epoxy resin type compound (B) used by this invention, the functional group which reacts with an acid functional group is only an epoxy group, and the compound which has 5 or more of this epoxy groups in 1 molecule is mentioned. It is done. Specific examples of such a compound include an epoxy in the molecular chain such as a phenol novolac epoxy resin synthesized by reacting phenol novolac and epichlorohydrin, a cresol novolac resin synthesized by reacting O-cresol novolak and epichlorohydrin. An epoxy resin compound having 5 or more groups is exemplified. Moreover, as a commercial item of such an epoxy resin, for example, as a bisphenol A type novolak epoxy resin, trade names of Mitsubishi Chemical Corporation: jER157S70, trade names of DIC Corporation: EPICLON N-865, N-885, Trade name of DIC Corporation as cresol novolac epoxy resin: EPICLON N-670, N-673, N-680, N-690, N-695, trade name of DIC Corporation as phenol novolac epoxy resin: N-770 N-775 and the like.

  Moreover, as an epoxy resin type compound (B), in addition to the epoxy resin type compound which has 5 or more of epoxy groups which react with the acid functional group of acid-modified polyolefin resin (A) in 1 molecule, it is 1 molecule of epoxy groups. An epoxy resin system having two or more functional groups in the molecule and having two or more functional groups that react with the acid functional groups of the acid-modified polyolefin resin (A), and the functional groups are epoxy groups and hydroxyl groups It may further contain a compound.

In the adhesive resin composition of the present invention, the acid functional group of the acid-modified polyolefin resin (A) and the functional group (epoxy group, hydroxyl group) of the epoxy resin compound (B) are adhesive functions to the adherend. By functioning as a base, it has excellent adhesion to various adherends such as metal, glass and plastic.
The epoxy resin compound (B) is preferably contained in the range of 1 to 15 parts by weight in 100 parts by weight of the solid content of the adhesive resin composition. The affinity of the acid-modified polyolefin resin (A) for the low-polarity plastic due to the polyolefin portion and the affinity for the dissimilar material such as metal and glass due to the adhesive functional group have a suitable balance. In addition to adhering to dissimilar materials such as glass, it also has excellent adhesive force when adhering to low-polarity plastics such as polyolefin.
Since the acid functional group of the acid-modified polyolefin resin (A) and the functional group (epoxy group, hydroxyl group) of the epoxy resin compound (B) easily react with each other by heating, they react with these other functional groups. It is not necessary to add a curing agent that can be used.

[Graft copolymer (G)]
In the adhesive resin composition of the present invention, the acid functional group of the acid-modified polyolefin resin (A) and the functional group (epoxy group, hydroxyl group) of the epoxy resin compound (B) are obtained by graft polymerization. It is preferable to contain the graft copolymer (G) obtained. According to the graft copolymer (G), the acid-modified polyolefin resin (A) and the epoxy resin-based compound (B) are graft-polymerized to prevent separation of the both, and the acid functional group and functional group. Due to the synergistic effect with the group (epoxy group, hydroxyl group), it can have excellent adhesive force.

The graft copolymer (G) preferably has an epoxy group derived from the epoxy resin compound (B). In this case, as the graft copolymer (G), an adhesive force improving effect by the epoxy group can be obtained together with the acid functional group and the functional group (epoxy group, hydroxyl group).
The graft copolymer (G) used in the present invention contains 85 to 99% by mass of the acid-modified polyolefin resin (A) and 1 to 15% by mass of the epoxy resin compound (B). Those obtained by graft polymerization are preferred.

The graft copolymer (G) is preferably obtained by melt graft polymerization of the acid-modified polyolefin resin (A) and the epoxy resin compound (B).
In the melt graft polymerization, the adhesive resin composition containing the acid-modified polyolefin resin (A) and the epoxy resin compound (B) is graft-polymerized in an apparatus by melt kneading. 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 in the graft copolymer (G) during the melt graft polymerization, it is desirable to remove and discharge volatile components that can react with the epoxy group, such as moisture, outside the apparatus.
When the acid-modified polyolefin resin (A) has an acid anhydride group as an acid functional group,
The reactivity with the functional group (epoxy group, hydroxyl group) of the epoxy resin compound (B) is high, and graft polymerization is possible under milder conditions, which is preferable.

The heating temperature at the time of melt-kneading is selected from the range of 130 to 300 ° C. in that the acid-modified polyolefin resin (A) and the epoxy resin compound (B) are sufficiently melted and not thermally decomposed. Is preferred. When the acid-modified polyolefin resin (A) is of a polypropylene type, 180 to 300 ° C. is preferable.
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-kneading apparatus.

[Thermoplastic elastomer resin (C)]
The adhesive resin composition of the present invention contains a thermoplastic elastomer resin (C) together with the acid-modified polyolefin resin (A) and the epoxy resin compound (B), or their graft copolymer (G). can do.
Examples of the thermoplastic elastomer resin (C) include styrene elastomer, styrene butadiene copolymer, epoxy-modified styrene butadiene copolymer, olefin elastomer, polyester elastomer, styrene butadiene styrene block copolymer, styrene ethylene propylene styrene block copolymer. Styrene isoprene butadiene styrene block copolymer, styrene isoprene styrene block copolymer, and the like.
When the thermoplastic elastomer resin (C) is added, the thermoplastic elastomer resin (C) is preferably contained within a range of 1 to 15 parts by weight in 100 parts by weight of the solid content of the adhesive resin composition. .

  As long as the thermoplastic elastomer resin (C) does not react with the acid-modified polyolefin resin (A) or the epoxy resin compound (B) under the conditions of melt kneading of the adhesive resin composition, It can also mix | blend before melt-kneading. In this case, when the mixture containing the acid-modified polyolefin resin (A), the epoxy resin compound (B), and the thermoplastic elastomer resin (C) is melt-kneaded, the acid-modified polyolefin resin (A) and the epoxy are mixed. An adhesive resin composition containing the graft copolymer (G) can be obtained by selectively reacting with the resin compound (B).

[Adhesive resin layer]
The adhesive resin composition of the present invention is obtained by melt-kneading the adhesive resin composition of the present invention, which contains the acid-modified polyolefin resin (A) and the epoxy resin compound (B) as essential components, and extrusion molding. It is possible to manufacture an adhesive resin layer by the method (one step) to do.
In the present invention, excellent adhesive strength can be obtained by the presence of the acid functional group of the acid-modified polyolefin resin (A) and the functional group (epoxy group, hydroxyl group) of the epoxy resin compound (B). In particular, even in a relatively low temperature range close to the melting point (Tm) of the acid-modified polyolefin resin (A), which is the base resin, excellent adhesive force can be obtained, and low-temperature adhesiveness is improved.

Further, since the acid-modified polyolefin resin (A) and the epoxy resin compound (B) can be graft-polymerized during the melt-kneading of the adhesive resin composition, the graft copolymer (G) It is not necessary to provide a separate preparation step, and the productivity is excellent, and damage to the resin component can be suppressed.
The adhesive resin composition of the present invention has excellent adhesion to various adherends such as metal, glass, plastic, etc., has a simple composition, and easily produces an adhesive resin layer. Is possible.
In the adhesive resin composition of the present invention, a filler, a colorant, an antioxidant, an antifoaming agent, a leveling agent, a light absorber, and the like can be appropriately added as other additives.

[Adherent]
Examples of adherends that can be bonded using the adhesive resin composition of the present invention include various adherends such as metal, glass, and plastic. The shape of the adherend is not particularly limited, and examples thereof include films, sheets, plates, panels, trays, rods (rod-like bodies), boxes, and cases.
Examples of the metal include steel, stainless steel, aluminum, copper, nickel, chromium and alloys thereof. Also, it can be applied to a composite material having a metal plating layer on the surface, and the base material for plating in that case is not particularly limited as long as it can be plated, and may be various materials such as metal, glass and plastic. Good.
Examples of the glass include alkali glass, non-alkali glass, and quartz glass.
Examples of the plastic include polyolefin resins such as high density polyethylene (HDPE), ultra high molecular weight polyethylene (UHMWPE), isotactic polypropylene, syndiotactic polypropylene, ethylene propylene copolymer resin; nylon 6 (N6), nylon 66 ( N66), nylon 46 (N46), nylon 11 (N11), nylon 12 (N12), nylon 610 (N610), nylon 612 (N612), nylon 6/66 copolymer (N6 / 66), nylon 6/66 / 610 copolymer (N6 / 66/610), nylon MXD6 (MXD6), nylon 6T, nylon 6 / 6T copolymer, nylon 66 / PP copolymer, nylon 66 / PPS copolymer, and other polyamide resins ; Polybutylene terephthalate (P T), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), PET / PEI copolymer, polyarylate (PAR), polybutylene naphthalate (PBN), liquid crystal polyester, polyoxyalkylene diimide diacid / polybutyrate Aromatic polyester resins such as terephthalate copolymer; polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylonitrile / styrene copolymer, methacrylonitrile / styrene / butadiene copolymer Polymer), polymethacrylate resins (for example, polynitrile resins such as polymethyl methacrylate (PMMA) and polyethyl methacrylate; vinyl acetate (EVA), polyvinyl alcohol (PVA), vinyl alcohol / Polyvinyl resins such as ethylene copolymer (EVOH), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride / vinylidene chloride copolymer, vinylidene chloride / methyl acrylate copolymer; .

[Adhesive resin molding]
The adhesive resin molded body of the present invention is a molded body formed from the adhesive resin composition of the present invention and having a shape such as a film or a sheet, and can be used as an adhesive resin film or an adhesive resin sheet. it can.
The adhesive resin molded article of the present invention is obtained by melt-kneading an adhesive resin composition containing the acid-modified polyolefin resin (A) and the epoxy resin compound (B) as essential components, and by extrusion molding, It can be manufactured by a method (one step) of forming into a shape such as a sheet.

The adhesive resin molded body of the present invention is laminated with an adherend, for example, by the methods described in the following (1) to (4) and heated, preferably by heating and pressurizing. It is possible to adhere to the kimono.
(1) A method of laminating and bonding an adhesive resin molded body on one surface of an adherend.
(2) A method of laminating and adhering different adhesive resin moldings to both surfaces of the adherend.
(3) A method of laminating and adhering different adherends to both surfaces of the adhesive resin molded body.
(4) A method in which a plurality of adhesive resin moldings and a plurality of adherends are alternately laminated and bonded.

[Adhesive resin laminate]
The adhesive resin laminate of the present invention is obtained by laminating an adhesive resin layer made of the adhesive resin composition of the present invention on at least one surface of a substrate. By providing the adhesive resin layer on one or both surfaces of the substrate, the adhesive resin layer can be used to adhere to the adherend. As a base material, it is not necessary to have adhesiveness in base material itself, and what can adhere | attach with the said adhesive resin layer is preferable. Similar to those exemplified as the adherend described above, various substrates such as metal, glass, and plastic can be used.

The adhesive resin laminate of the present invention is obtained by melt-kneading an adhesive resin composition containing the acid-modified polyolefin resin (A) and the epoxy resin compound (B) as essential components, and extruding the adhesive. It can be manufactured by a method (one step) of forming a conductive resin layer.
When the substrate is made of a thermoplastic resin, the adhesive resin composition can be extruded by a coextrusion method. It is also possible to perform extrusion molding of the adhesive resin composition by an extrusion laminating method.

When the adhesive resin laminate of the present invention has the adhesive resin layer only on one side of the base material, the adhesive resin laminate is laminated with the adherend by the method described in (1) or (2) above, for example. It is possible to bond to various adherends by heating, preferably by heating and pressing.
Moreover, when the adhesive resin laminated body of this invention has the said adhesive resin layer on both surfaces of a base material, it is laminated | stacked with a to-be-adhered body by the method as mentioned in said (1)-(4), for example. Then, it is possible to adhere to various adherends by heating, preferably by heating and pressing.

  Hereinafter, the present invention will be specifically described with reference to examples.

(Adhesive resin film)
Adhesive resin films of the examples and comparative examples were produced with the compositions shown in Table 1. The production of the adhesive resin film was carried out by a method in which an acid-modified polyolefin resin, an epoxy group-containing resin and an elastomer resin were first melt-kneaded and then formed into a film having a predetermined thickness by extrusion molding.

(Evaluation method of adhesive strength)
In accordance with JIS Z 1526, the adhesive strength of the heat seal part of the adhesive resin film to various adherends was measured at a tensile speed of 300 mm / min and a width of 15 mm.
The heat sealing condition is to heat and pressurize at a pressure of 0.2 MPa for 3 seconds or 7 seconds at any temperature of 140 ° C., 160 ° C., and 180 ° C.
The thickness of the adherend is 200 μm for aluminum plates, copper / nickel plated plates, glass plates, and SUS plates. In the case of a corona-treated nylon film, the thickness is 25 μm.
When the adherend was an aluminum plate, a copper / nickel plated plate, a glass plate, or a corona-treated nylon film, the heat seal time was 3 seconds. Moreover, when the adherend was a SUS plate (SUS: a kind of stainless steel), the heat sealing time was 7 seconds.

Table 1 shows the composition (unit: mass%) of the film resin.
In addition, the meaning of the abbreviation used in Table 1 is as follows.
“MAH-PP”: maleic anhydride-modified polypropylene (ρ = 0.896 g / cm ³ , Tm = 140 ° C., MFR = 7.0)
“Epoxy group-containing resin (1)”: “YP-55U” of phenoxy resin (bisphenol A type, weight average molecular weight 40000-45000, manufactured by Nippon Steel Chemical Co., Ltd., trade name) (functional group in one molecule The number of hydroxyl groups is estimated to be 140 to 160 hydroxyl groups and two epoxy groups)
“Elastomer resin”: Epoxy-modified styrene-butadiene copolymer “Epofriend AT501” (epoxy compound of styrene-butadiene block copolymer, manufactured by Daicel Chemical Industries, Ltd., trade name)
“Epoxy group-containing resin (2)”: “Epicoat 1010” of epoxy resin (bisphenol A type, weight average molecular weight 5500, product name, manufactured by Mitsubishi Chemical Corporation) (the number of functional groups in one molecule is a hydroxyl group Estimated 17 and 2 epoxy groups)
"Epoxy group-containing resin (3)" ... "Epicoat 1001" of epoxy resin (bisphenol A type, weight average molecular weight 900, product name, manufactured by Mitsubishi Chemical Corporation) (the number of functional groups in one molecule is a hydroxyl group Estimated 2 and 2 epoxy groups)
“Epoxy group-containing resin (4)”: “jER157S70” of epoxy resin (bisphenol A type novolak type, weight average molecular weight 900, trade name, manufactured by Mitsubishi Chemical Corporation) (the number of functional groups in one molecule is Estimated 6 epoxy groups, 0 hydroxyl groups)

As shown in Tables 2-6, according to Examples 1-6 of the present invention, in an adhesive resin film having maleic anhydride-modified polypropylene as a base resin (main component), a functional group that reacts with an acid functional group ( In the case of only maleic anhydride-modified polypropylene (Comparative Example 1) by using an epoxy group-containing resin (1) having a large number (5 or more) of epoxy groups and hydroxyl groups in one molecule and an epoxy group-containing resin (2). ) Or an epoxy group-containing resin (3) having a small number of functional groups in one molecule, a higher adhesive strength was obtained than when blended (Comparative Example 2). In particular, the adhesive strength when heat sealed at 140 ° C. or 160 ° C., which is comparable to the Tm of MAH-PP used, is relatively low, and can be applied to various adherends such as metal, glass, and plastic. On the other hand, it was found to have excellent low-temperature adhesion.
Further, according to Example 7 of the present invention, in an adhesive resin film having maleic anhydride-modified polypropylene as a base resin (main component), a large number of functional groups (epoxy groups) that react with acid functional groups per molecule. By using the epoxy group-containing resin (4) having (5 or more), only the maleic anhydride-modified polypropylene (Comparative Example 1) or an epoxy group-containing resin (3 with a small number of functional groups in one molecule) ) Was blended (Comparative Example 2) higher adhesive strength was obtained. In particular, the adhesive strength when heat sealed at 140 ° C. or 160 ° C., which is comparable to the Tm of MAH-PP used, is relatively low, and can be applied to various adherends such as metal, glass, and plastic. On the other hand, it was found to have excellent low-temperature adhesion.

  The present invention has an excellent adhesive force to various adherends such as metal, glass, plastic, etc., has an easy composition, and can be easily manufactured. Adhesive resin composition, adhesive resin Since a molded body and an adhesive resin laminate can be provided, the industrial utility value is great.

Claims (5)

An acid-modified polyolefin resin (A) from which unreacted acid functional group-containing monomers have been removed, and an acid having two or more epoxy groups in one molecule and from which the unreacted acid functional group-containing monomers have been removed Adhesiveness which does not contain a radical generator and an epoxy resin compound (B) having 5 or more functional groups in one molecule which react with the acid functional group of the modified polyolefin resin (A) as an essential component An adhesive resin film formed from a resin composition,
In the adhesive resin composition, the acid functional group of the acid-modified polyolefin resin (A) from which the unreacted acid functional group-containing monomer is removed and the functional group of the epoxy resin compound (B) are grafted. Containing a graft copolymer (G) obtained by polymerization,
The unreacted acid functional group-containing monomer is removed the acid-modified polyolefin resin (A), unreacted acid functional group-containing monomer is acid-modified polypropylene-based resin has been removed, or unreacted acid functional group-containing monomer Removed acid-modified polyethylene resin,
The adhesive resin film, wherein the adhesive resin film has a heat sealing temperature of 140 ° C to 180 ° C. The adhesive resin film according to claim 1 , wherein the functional group of the epoxy resin compound (B) is an epoxy group and a hydroxyl group, or only an epoxy group. The adhesiveness according to claim 1 or 2 , wherein the epoxy resin compound (B) is contained in the range of 1 to 15 parts by weight in 100 parts by weight of the solid content of the adhesive resin composition. Resin film. The thermoplastic elastomer resin (C) is further added so as to be contained in a range of 1 to 15 parts by weight in 100 parts by weight of the solid content of the adhesive resin composition. The adhesive resin film in any one of 1-3 . The adhesive resin laminated body by which the adhesive resin film in any one of Claims 1-4 is laminated | stacked on the at least single side | surface of a base material.