JP6875462B2 - Adhesive resin film and adhesive resin laminate - Google Patents

Description

The present invention relates to an adhesive resin film having excellent adhesive strength 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 having various surface treatments such as plating on the metal plate, for example, laminating with a metal. Films for use are known (Patent Document 1). Further, as an adhesive resin for a glass plate, an interlayer film for laminated glass is known (Patent Document 2).

Patent Document 1 discloses a laminated film for metal lamination, which comprises an adhesive layer made of an unsaturated carboxylic acid-modified polypropylene resin and one or more stretched polypropylene resin layers.
However, in Patent Document 1, as the heat sealing condition with the 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. by the heat sealer. As described above, in the prior art, even if thermocompression bonding is performed at a high temperature, excellent adhesive strength is not obtained. Therefore, there is a problem that improvement is required to further improve the adhesive strength.

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. It is said that it can be obtained.
However, the resin composition disclosed in Patent Document 2 has a problem that if the content of the acid-modified polyolefin exceeds 5 parts by weight, sufficient adhesive strength between the interlayer film for laminated glass and the glass plate cannot be obtained. It was.

JP-A-2002-192672 Japanese Unexamined Patent Publication No. 2009-184887

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

In view of the above situation, the present invention has an excellent adhesive force to various adherends such as metal, glass, and plastic, has a simple composition, and is an easily manufacturable 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 an unreacted acid-functional group-containing monomer has been removed, and two or more epoxy groups in one molecule, and the unreacted one. The epoxy resin compound (B) having 5 or more functional groups in one molecule that reacts with the acid functional groups of the acid-modified polyolefin resin (A) from which the acid functional group-containing monomer of the above has been removed is graft-polymerized. An adhesive resin composition containing the obtained graft copolymer (G) (excluding the graft copolymer obtained by graft-polymerizing a polyamide resin) is melt-kneaded and then extruded. According to JIS Z 1526, the adhesive resin film is heat-sealed on a glass plate at a temperature of 140 ° C. at a pressure of 0.2 MPa for 3 seconds, and a tensile speed of 300 mm / Provided is an adhesive resin film characterized in that the adhesive strength measured at a width of 15 mm is 25.6 N / 15 mm or more.
It is preferable that 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.
The present invention also provides an adhesive resin laminate in which the adhesive resin film is laminated on at least one surface of a base material.

According to the present invention, an adhesive resin film having excellent adhesive strength to various adherends such as metal, glass, and plastic, having a simple composition, and being easily manufactured, and adhesive. It becomes possible to provide a sex 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) and two or more epoxy groups in one molecule, and has a functionality that reacts with the acid functional group of the acid-modified polyolefin resin (A). An epoxy resin compound (B) having 5 or more groups in one molecule is an essential component.

[Acid-modified polyolefin resin (A)]
The acid-modified polyolefin resin (A) used in the present invention is a polyolefin-based resin modified with an unsaturated carboxylic acid or a derivative thereof, and has a carboxyl group or an anhydrous carboxylic acid group in the polyolefin-based resin. Preferably, the polyolefin-based 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, or acid functionality. 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 them, polypropylene-based resins such as homopolypropylene (homo-PP, propylene homopolymer), propylene-ethylene block copolymer (blockPP), and propylene-ethylene random copolymer (random PP) are preferable. In particular, random PP is preferable.
Examples of the olefins in the case of copolymerization include olefin-based 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 a carboxylic acid anhydride group in the same molecule, and is a various unsaturated monocarboxylic acid, dicarboxylic acid, or dicarboxylic acid. Consists 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, and tetrahydrophthalic acid. , Α, β-unsaturated carboxylic acid monomers such as endo-bicyclo [2.2.1] -5-heptene-2,3-dicarboxylic acid (endic acid).
Examples of the acid functional group-containing monomer having a carboxylic acid anhydride group (carboxylic acid anhydride group-containing monomer) include unsaturated dicarboxylic acids such as maleic anhydride, nadicic anhydride, itaconic anhydride, citraconic anhydride, and endic anhydride. Anhydride monomer can be mentioned.
One type of these acid functional group-containing monomers may be used in the acid-modified polyolefin resin (A), or two or more types may be used in combination.

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

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

[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 molecule of a 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.
The epoxy resin-based compound (B) includes a polymer having a large number of hydroxyl groups, such as polyhydroxypolyester, polyhydroxypolyester, polyhydroxypolyester, and polyhydroxypolypolymer, which is epoxidized by glycidylation or the like into one molecule. Examples thereof include compounds having two or more epoxy groups. Specific examples thereof include an epoxy resin compound represented by the following general formula (1), which is a phenoxy resin synthesized by reacting bisphenols with epichlorohydrin and having epoxy groups at both ends. Be done.

In the general formula (1), examples of the substituents R and R'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 groups that react with the acid functional groups of the acid-modified polyolefin resin (A) are p hydroxyl groups and two epoxy groups at both ends. In order to increase the number of functional groups that react with acid functional groups to 5 or more in one molecule, it is preferable that p + 2 ≧ 5.
The phenoxy resin is a 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 copolymerized phenoxy resin, one of R and R'is CH ₃ and the other is H. Examples include phenoxy resin. Further, since the bisphenol type epoxy resin is represented by the above general formula (1) like the phenoxy resin, a resin having a relatively high molecular weight and a large number of hydroxyl groups p can be selected and used.

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 preferably 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 bisphenol A type, the number of hydroxyl groups p is about 70), and higher molecular weight ones can also be used.
The upper limit of the average molecular weight of the phenoxy resin or the epoxy resin is not particularly limited, but is preferably about 80,000 (in the case of the bisphenol A type, the number of hydroxyl groups p is about 280). When the average molecular weight of the phenoxy resin or epoxy resin is determined by GPC, for example, tetrahydrofuran (THF) is used as the eluent for GPC, and TSKgel G4000H and TSKgel G3000H (both manufactured by Tosoh Corporation) are used as columns. It can be obtained by concatenating the product name).

Examples of such a phenoxy resin include trade names: YP-50 (Mw is 60,000 to 80,000, BPA type, number of hydroxyl groups p is about 210 to 280) and YP-50S (manufactured by Nippon Steel Chemical Co., Ltd.). Mw is 50,000 to 70,000, BPA type, number of hydroxyl groups p is about 175 to 245), YP-55U (Mw is 40,000 to 45,000, BPA type, number of hydroxyl groups is about 140 to 160), YP-70 (Mw is 50,000 to 60,000, BPA / BPF copolymer type), ZX-1356-2 (Mw is 60,000 to 80,000, BPA / BPF copolymer type), FX-316 ( Mw is 40,000 to 60,000, BPF type), etc .; Phenoxy type grade 1256 (molecular weight about 50,000, BPA type), 4250 (molecular weight about 60,000, BPA / BPF copolymer type), manufactured by Mitsubishi Chemical Corporation. 4275 (molecular weight about 60,000, BPA / BPF copolymerized type), 1255HX30, YX8100BH30, YX6954BH30, etc .; PKHB, PKHC, PKHH, PKHJ, etc. manufactured by Tomoe Kogyo Co., Ltd.
As the epoxy resin, trade name: YD-020G (epoxy equivalent 3,000 to 4500, BPA type) manufactured by Nippon Steel Chemical Co., Ltd .; grade 1010 (average molecular weight 5500, BPA type, epoxy) manufactured by Mitsubishi Chemical Co., Ltd. Equivalent 3000 to 5000), 1009 (average molecular weight 3800, BPA type, epoxy equivalent 2400 to 3300) and the like.

The epoxy resin compound (B) used in the present invention includes a compound in which the only functional group that reacts with the acid functional group is an epoxy group and the epoxy group has 5 or more in one molecule. Be done. Specific examples of such compounds include phenol novolac epoxy resin synthesized by reacting phenol novolac with epichlorohydrin, and cresol novolac resin synthesized by reacting O-cresol novolac with epichlorohydrin, and the like. Examples thereof include epoxy resin compounds having 5 or more groups. Commercially available products of such epoxy resins include, for example, bisphenol A type novolak epoxy resin, trade name: jER157S70 manufactured by Mitsubishi Chemical Corporation, trade name: EPICLON N-865, N-885, and DIC Corporation. As a cresol novolac epoxy resin, DIC Corporation's trade name: EPICLON N-670, N-673, N-680, N-690, N-695, as a phenol novolac epoxy resin, DIC Corporation's trade name: N-770 , N-775 and the like.

The epoxy resin-based compound (B) includes one molecule of epoxy group in addition to the epoxy resin-based compound having five or more epoxy groups in one molecule that react with the acid functional group of the acid-modified polyolefin resin (A). An epoxy resin system having two or more functional groups in one molecule and having five or more functional groups in one molecule that react with the acid functional group of the acid-modified polyolefin resin (A), the functional groups being an epoxy group and a hydroxyl group. 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) have adhesive functionality to the adherend. By functioning as a base, it has excellent adhesive strength 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 polyolefin portion of the acid-modified polyolefin resin (A) for a plastic having low polarity and the affinity of the adhesive functional group for different materials such as metal and glass have a suitable balance, and the metal and the like have a suitable balance. It has excellent adhesive strength not only when adhering to different materials such as glass, but also 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 also react with these functional groups. It is not necessary to add a possible curing agent or the like.

[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) to be 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 their separation from each other, and the acid functional group and the functional group are functional. Due to the synergistic effect with the group (epoxy group, hydroxyl group), it is possible to have excellent adhesive strength.

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

The graft copolymer (G) is preferably obtained by melt-grafting polymerizing the acid-modified polyolefin resin (A) and the epoxy resin-based compound (B).
In this melt graft polymerization, the adhesive resin composition containing the acid-modified polyolefin resin (A) and the epoxy resin-based compound (B) is graft-polymerized in an apparatus by melt-kneading. As the melt-kneading device, a single-screw extruder, a multi-screw extruder, a Banbury mixer, a plast mill, a heating 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 the volatile components that can react with the epoxy group, such as water, to the outside of the apparatus.
When the acid-modified polyolefin resin (A) has an acid anhydride group as an acid functional group, the epoxy resin compound (B) has a high reactivity with a functional group (epoxy group, hydroxyl group) and is more mild. It is preferable because graft polymerization is possible under the conditions.

The heating temperature during melt-kneading should be selected from the range of 130 to 300 ° C. in that the acid-modified polyolefin resin (A) and the epoxy resin-based compound (B) are sufficiently melted and do not thermally decompose. Is preferable. When the acid-modified polyolefin resin (A) is polypropylene-based, 180 to 300 ° C. is preferable.
The kneading temperature can be measured by a method such as bringing a thermocouple into contact with the adhesive resin composition in a molten state immediately after being extruded from the melt-kneading apparatus.

[Thermoplastic elastomer resin (C)]
The adhesive resin composition of the present invention contains the thermoplastic elastomer resin (C) together with the acid-modified polyolefin resin (A) and the epoxy resin-based compound (B), or a graft copolymer (G) thereof. 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, and 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, it is preferable 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. ..

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

[Adhesive resin layer]
The adhesive resin composition of the present invention is extruded by melt-kneading the adhesive resin composition of the present invention containing the acid-modified polyolefin resin (A) and the epoxy resin-based compound (B) as essential components. It is possible to produce an adhesive resin layer by the method (1 step).
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, excellent adhesive strength can be obtained and low-temperature adhesiveness is improved even in a relatively low temperature region close to the melting point (Tm) of the acid-modified polyolefin resin (A), which is the base resin.

Further, when the adhesive resin composition is melt-kneaded, the acid-modified polyolefin resin (A) and the epoxy resin-based compound (B) can be graft-polymerized, so that the graft copolymer (G) can be graft-polymerized. It is not necessary to separately provide a preparation process for the resin, which is excellent in productivity and can suppress damage to the resin component.
The adhesive resin composition of the present invention has excellent adhesive strength to various adherends such as metal, glass, and plastic, has a simple composition, and easily produces an adhesive resin layer. It is possible.
In the adhesive resin composition of the present invention, as other additives, a filler, a colorant, an antioxidant, an antifoaming agent, a leveling agent, a light absorber and the like can be appropriately added.

[Subject]
Examples of the adherend that can be adhered 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 a film, a sheet, a plate, a panel, a tray, a rod (rod-shaped body), a box body, and a housing.
Examples of the metal include steel, stainless steel, aluminum, copper, nickel, chromium and alloys thereof. Further, 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 plating is possible, and various materials such as metal, glass, and plastic may be used. Good.
Examples of the glass include alkaline glass, non-alkali glass, and quartz glass.
Examples of plastics include polyolefin resins such as high-density polyethylene (HDPE), ultra-high molecular weight polyethylene (UHMWPE), isotactic polypropylene, syndiotactic polypropylene, and ethylene-propylene copolymer resin; nylon 6 (N6) and 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 Polyamide-based resins such as / 610 copolymer (N6 / 66/610), nylon MXD6 (MXD6), nylon 6T, nylon 6 / 6T copolymer, nylon 66 / PP copolymer, nylon 66 / PPS copolymer, etc. Polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), PET / PEI copolymer, polyallylate (PAR), polybutylene naphthalate (PBN), liquid crystal polyester, polyoxyalkylene diimide di Aromatic polyester resins such as acid / polybutyrate terephthalate copolymers; polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylonitrile / styrene copolymer, methacrylonitrile / Steryl / butadiene copolymer), polymethacrylate-based resin (for example, polynitrile-based resin such as polymethylmethacrylate (PMMA), polyethyl methacrylate; vinyl acetate (EVA), polyvinyl alcohol (PVA), vinyl alcohol / ethylene Copolymers (EVOH), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride / vinylidene chloride copolymers, vinylidene chloride / methyl acrylate copolymers and other polyvinyl-based resins; and the like.

[Adhesive resin molded product]
The adhesive resin molded product of the present invention is a molded product 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, an adhesive resin sheet or the like. it can.
In the adhesive resin molded product of the present invention, an adhesive resin composition containing the acid-modified polyolefin resin (A) and the epoxy resin compound (B) as essential components is melt-kneaded and extruded to form a film. It can be manufactured by a method (one step) of molding into a shape such as a sheet.

The adhesive resin molded product of the present invention is laminated with an adherend by, for example, the methods listed in (1) to (4) below, and is subjected to various types of coatings by heating, preferably by heating and pressurizing. It is possible to adhere to the body.
(1) A method of laminating and adhering an adhesive resin molded body on one side of an adherend.
(2) A method of laminating and adhering different adhesive resin molded bodies to both sides of an adherend.
(3) Adhesive A method of laminating and adhering different adherends to both sides of a resin molded body.
(4) A method in which a plurality of adhesive resin molded bodies and a plurality of adherends are alternately laminated and bonded.

[Adhesive resin laminate]
The adhesive resin laminate of the present invention is formed by laminating an adhesive resin layer made of the adhesive resin composition of the present invention on at least one surface of a base material. By providing the adhesive resin layer on one side or both sides of the base material, the adhesive resin layer can be used to adhere to the adherend. The base material does not have to have adhesiveness to the base material itself, and is preferably one that can be adhered to the adhesive resin layer. Similar to the above-exemplified adherends, various base materials such as metal, glass, and plastic can be mentioned.

In the adhesive resin laminate of the present invention, the adhesive resin composition containing the acid-modified polyolefin resin (A) and the epoxy resin-based compound (B) as essential components is melt-kneaded, and the adhesive is bonded by extrusion molding. It can be manufactured by the method of molding the sex resin layer (1 step).
When the base material is made of a thermoplastic resin, extrusion molding of the adhesive resin composition can be performed by a coextrusion method. It is also possible to extrude the adhesive resin composition by an extrusion laminating method.

When the adhesive resin laminate of the present invention has the adhesive resin layer on only one side of the base material, it is laminated with the adherend by, for example, the method described in (1) or (2) above. By heating, preferably by heating and pressurizing, it is possible to adhere to various adherends.
When the adhesive resin laminate of the present invention has the adhesive resin layers on both sides of the base material, it is laminated with the adherend by, for example, the methods described in (1) to (4) above. However, it is possible to adhere to various adherends by heating, preferably by heating and pressurizing.

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

(Adhesive resin film)
Adhesive resin films of each Example and Comparative Example were produced according to the compositions shown in Table 1. The adhesive resin film was first produced by melt-kneading an acid-modified polyolefin resin, an epoxy group-containing resin and an elastomer resin, and then forming a film having a predetermined thickness by extrusion molding.

(Evaluation method of adhesive strength)
According to JIS Z 1526, the adhesive strength of the heat-sealed portion 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 seal condition is to heat and pressurize at a pressure of 0.2 MPa for 3 seconds or 7 seconds at any of 140 ° C., 160 ° C., and 180 ° C.
The thickness of the adherend is 200 μm for the aluminum plate, the copper / nickel plated plate, the glass plate, and the SUS plate. In the case of the 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 set to 3 seconds. When the adherend was a SUS plate (SUS: a type of stainless steel), the heat seal time was set to 7 seconds.

Table 1 shows the composition (unit: mass%) of the film resin.
The meanings of the abbreviations used in Table 1 are as follows.
"MAH-PP" ... Maleic anhydride-modified polypropylene (ρ = 0.896 g / cm ³ , Tm = 140 ° C., MFR = 7.0)
"Epoxide group-containing resin (1)": Phenoxy resin "YP-55U" (bisphenol A type, weight average molecular weight 40,000-45,000, 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, and the number of epoxy groups is 2.)
"Elastomer resin": Epoxy-modified styrene-butadiene copolymer "Epofriend AT501" (epoxy compound of styrene-butadiene block copolymer, manufactured by Daicel Chemical Industry Co., Ltd., trade name)
"Epoxy group-containing resin (2)" ... Epoxy resin "Epicoat 1010" (bisphenol A type, weight average molecular weight 5500, manufactured by Mitsubishi Chemical Corporation, trade name) (The number of functional groups in one molecule is a hydroxyl group. Estimated 17 pieces, 2 epoxy groups)
"Epoxy group-containing resin (3)": Epoxy resin "Epicoat 1001" (bisphenol A type, weight average molecular weight 900, manufactured by Mitsubishi Chemical Corporation, trade name) (The number of functional groups in one molecule is hydroxyl group. 2 estimated, 2 epoxy groups)
"Epoxy group-containing resin (4)" ... Epoxy resin "jER157S70" (bisphenol A type novolac type, weight average molecular weight 900, manufactured by Mitsubishi Chemical Corporation, trade name) (The number of functional groups in one molecule is Epoxy group is estimated to be 6 and hydroxyl group is 0)

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

The present invention has an excellent adhesive force to various adherends such as metal, glass, and plastic, has a simple composition, and is an easily manufacturable adhesive resin composition and adhesive resin. Since it is possible to provide a molded body and an adhesive resin laminate, it has great industrial utility value.

Claims (3)

An acid-modified polyolefin resin (A) from which an unreacted acid-functional group-containing monomer has been removed, and an acid having two or more epoxy groups in one molecule and from which the unreacted acid-functional group-containing monomer has been removed. functional groups reactive with the acid functional groups of the modified polyolefin resin (a), the epoxy resin compound having 5 or more in one molecule and (B), but a graft copolymer obtained through graft polymerization (G) ( However, this is an adhesive resin film formed by extrusion-molding an adhesive resin composition containing a graft copolymer obtained by graft-polymerizing a polyamide resin) after melt-kneading.
According to JIS Z 1526, the adhesive resin film was heat-sealed on a glass plate at a temperature of 140 ° C. at a pressure of 0.2 MPa for 3 seconds, and measured at a tensile speed of 300 mm / min and a width of 15 mm. An adhesive resin film having an adhesive strength of 25.6 N / 15 mm or more. The adhesive resin film according to claim 1, wherein the epoxy resin-based compound (B) is contained in the solid content of 100 parts by weight of the adhesive resin composition in the range of 1 to 15 parts by weight. .. An adhesive resin laminate obtained by laminating the adhesive resin film according to claim 1 or 2 on at least one surface of a base material.