JPS647623B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an adhesive resin composition whose main component is a modified olefinic polymer containing an unsaturated carboxylic acid or its anhydride. As is well known, polyolefins such as polyethylene and polypropylene have various excellent physical and chemical properties, mechanical properties, and moldability. Widely used in industrial fields. However, since these polyolefins are nonpolar, they have poor adhesion to different materials such as metals, glass, and polar polymeric materials, and have the disadvantage that it is difficult to form composites with these various materials. In order to improve this drawback, methods have been known to impart adhesive properties by introducing polar groups through copolymerization of ethylene and acrylic acid, or graft modification of polyolefins with acrylic acid or maleic anhydride. There is. In addition, various polyolefin compositions and methods for producing the same have been proposed for the purpose of further improving adhesion to metals, polymeric materials, and the like. For example, a composition obtained by adding an unsaturated carboxylic acid anhydride such as maleic anhydride and a metal compound such as magnesium oxide to polyolefin and graft-modifying it while melting (Japanese Patent Publication No. 51-48195
Publication No. 49-98484, Japanese Patent Publication No. 1977-98484
10837), compositions made by adding metal oxides such as magnesium oxide to polyolefin graft-modified with acrylic acid or maleic anhydride (JP-A-51-23544, JP-A-52-121059) ,
Compositions of polypropylene graft-modified with unsaturated carboxylic anhydrides and ethylene polymers (JP-A-52-14684, JP-A-52-26548,
JP-A-56-21850), a composition comprising a propylene polymer graft-modified with an unsaturated carboxylic anhydride, an amorphous propylene polymer, and an ethylene polymer (JP-A-54-90346) Publication No.),
In addition, there are many polyolefin adhesive resins such as compositions of ethylene copolymers and styrene polymers containing polar groups such as carboxyl groups (Japanese Unexamined Patent Applications No. 134732/1982, 143039/1983). Compositions are known. It is also well known that these resin compositions are generally widely used as coating agents, binders, or lamination adhesives for various inorganic and organic materials such as metals, glass, and polymeric materials. By the way, recently, in the field of resin molding processing, in order to reduce processing costs through energy saving and high-speed processing, lower temperature,
Moreover, there is a strong desire for a resin that can be easily bonded in a short period of time. However, the adhesive strength of conventional adhesive resin compositions is insufficient, and at present no one has been found that can satisfy the above requirements. In view of these circumstances, the inventors of the present invention have conducted intensive studies to obtain a resin composition that can be easily bonded at low temperatures and in a short time. They discovered a composition and led to the present invention. That is, the present invention provides a modified olefinic polymer (A) containing an unsaturated carboxylic acid or its anhydride, or a modified olefinic polymer (A) and an unmodified olefinic polymer (B).
100 parts by weight of a polymer composition consisting of (meth)acrylic acid ester and/or styrenic polymer
(C) 2 to 50 parts by weight, and from oxides, hydroxides, phosphates, carbonates, and carboxylates of metals of groups 1, 2, of the periodic table of elements with a median diameter of 10μ or less Selected metal compounds (D)0.01~10
The present invention relates to an adhesive resin composition consisting of parts by weight. Here, the adhesive resin composition of the present invention has the feature that it not only has easy adhesion as described above, but also has an extremely strong durable adhesive force regardless of large fluctuations in usage environmental conditions. Because of these properties, coatings, laminates, filler-reinforced resins, etc. manufactured using the adhesive resin composition of the present invention are suitable for use in vehicle parts, ship parts, aircraft parts, civil engineering and construction materials, and electrical parts. Can be widely used as furniture, office supplies, packaging materials. For example, covering steel pipes; aluminum laminated sheath cables for communications; or sandwich laminates with steel plates, stainless steel, aluminum, etc. for weight reduction, vibration damping, sound insulation, etc., for car bodies, bonnets, fenders, dart boards, etc. Automotive parts such as floors, air cleaner cases, oil pans, seat frames, trims, and sunroof panels; electrical parts such as refrigerators, washing machines, audio equipment, and air conditioners; building materials such as doors, shutters, walls, roofs, soundproof fences, elevator interiors, etc. , office supplies such as office desks, cabinets, and lockers, containers such as trunks, containers, and rice bins; other filler-reinforced resins such as glass fiber, or polyamide, polyurethane, polyester, ethylene-vinyl alcohol copolymer, polyethylene, and ethylene. -Vinyl acetate copolymer, polypropylene, etc. Can be effectively used as a packaging material etc. by laminating these together. The present invention will be explained in detail below. The modified olefin polymer (A) containing an unsaturated carboxylic acid or its anhydride, which is one of the main components of the adhesive resin composition of the present invention, is produced by a direct copolymerization method or a graft copolymerization method. and include the following: For example, acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, hymic acid, bicyclo(2,2,
2) oct-5-ene-2,3-dicarboxylic acid,
4-methylcyclohex-4-ene-1,2 dicarboxylic acid, 1,2,3,4,5,8,9,10-octahydronaphthalene-2,3-dicarboxylic acid,
Bicyclo(2,2,1)oct-7-ene-2,
Direct copolymers of unsaturated carboxylic acids and their anhydrides such as 3,5,6-tetracarboxylic acid and 7-oxabicyclo(2,2,1)hept-5-ene-2,3dicarboxylic acid with ethylene. , or these in addition to methyl (meth)acrylate, (meth)
Unsaturated carboxylic acid derivatives such as ethyl acrylate, n-butyl (meth)acrylate, tertiary butyl (meth)acrylate, acrylamide, maleic acid mono- or diester, vinyl esters such as vinyl acetate and vinyl propionate, propylene, Butene-1, 4-methylpentene-1, styrene,
Examples include those obtained by copolymerizing copolymerizable monomers such as unsaturated hydrocarbons such as α-methylstyrene and chlorostyrene, and derivatives thereof. These polymers can be produced by a known high-pressure polymerization method or solution polymerization method. Also included are graft copolymers of the above-mentioned unsaturated carboxylic acids and their anhydrides, and other copolymerizable monomers used as necessary, and olefinic polymers. Examples of the olefinic polymer that is the base of this graft copolymer include low density polyethylene, linear low density polyethylene, high density polyethylene, crystalline or amorphous polypropylene, crystalline or amorphous propylene-ethylene random copolymer, etc. Polymer, crystalline or amorphous propylene-ethylene block copolymer, ethylene-propylene-nonconjugated diene terpolymer, polybutene-1, propylene-butene-1 copolymer, poly-4-methylpentene- 1,
propylene-4-methylpentene-1 copolymer,
Propylene-ethylene-butene-1 terpolymer, ethylene-vinyl acetate copolymer, ethylene-
(meth)methyl acrylate copolymer, ethylene-
(meth)ethyl acrylate copolymer, ethylene-
(meth)butyl acrylate copolymer, ethylene-
(meth)acrylic acid or its partial metal salt copolymer, ethylene-(meth)acrylic acid-(meth)acrylic acid ester copolymer, ethylene-vinyl alcohol copolymer, ethylene-vinyl acetate-vinyl alcohol copolymer Various olefin homopolymers and copolymers such as ethylene-styrene copolymers and the like can be used. Moreover, two or more types of these olefin polymers can also be used in combination. Further, the above-mentioned graft copolymer can be produced by a known melt-kneading method, solution modification method, slurry-based heterogeneous modification method, or powder state modification method. The content of unsaturated carboxylic acid or unsaturated carboxylic acid anhydride in the olefinic polymer containing unsaturated carboxylic acid or unsaturated carboxylic acid anhydride is preferably in the range of 0.01 to 400 mmol per 100 g of the polymer. If the content is less than 0.01 mmol, there is no significant effect of improving adhesion. On the other hand, even if its content is higher than 400 mmol,
Regarding adhesion, no more significant effect is exhibited. A particularly preferred range of its content is 0.1 to 300 mmol. Further, the preferable range of the melt index of the olefin polymer (A) is
It is between 0.2 and 500. Note that two or more types of these olefin polymers can also be used in combination. In the present invention, a polymer composition comprising a modified olefin polymer (A) containing the above-mentioned unsaturated carboxylic acid or its anhydride and an unmodified olefin polymer (B) can also be used as an adhesive resin composition. used as an ingredient. As the unmodified olefin polymer (B), for example, one selected from the olefin polymers used as the base of the graft copolymer mentioned above is used. The melt index of the polymer is preferably from 0.1 to 100. here,
The content of unsaturated carboxylic acid or its anhydride in 100 g of the polymer composition consisting of the modified olefin polymer (A) and the unmodified olefin polymer (B) is
It is desirable that the amount be 0.01 mmol or more. If the amount is less than 0.01 mmol, the adhesive effect will not be sufficient. The (meth)acrylic acid ester polymer used as one of the other active ingredients (C) of the adhesive resin composition of the present invention is, for example, methyl (meth)acrylate, ethyl (meth)acrylate, ( Propyl (meth)acrylate, butyl (meth)acrylate, (meth)
Homopolymers such as hexyl acrylate, 2-hydroxyethyl (meth)acrylate, and dimethylaminoethyl (meth)acrylate, or copolymers thereof, as well as their (meth)acrylic esters, acrylic acid, and methacrylic acid. , maleic acid and its derivatives, styrene, α-methylstyrene, o-chlorostyrene, p-chlorostyrene,
It is a polymer containing a (meth)acrylic acid ester component, such as a binary or multicomponent copolymer with acrylonitrile, vinyl acetate, etc. Among these, methyl methacrylate polymers and copolymers containing the same as main components are preferred. In addition, styrenic polymers include, for example, styrene,
Homopolymers of α-methylstyrene, o-ethylstyrene, vinyltoluene, o-chlorostyrene, p-chlorostyrene, etc., or copolymers thereof, as well as these styrene monomers and acrylonitrile, methacrylonitrile, α -Chloroacrylonitrile, vinylidene cyanide, (meth)acrylic acid, the above (meth)acrylic acid esters, maleic acid and its derivatives, itaconic acid and its derivatives, hymic acid and its derivatives, vinyl acetate, vinyl chloride, vinylidene chloride ,
It is a polymer containing a styrenic monomer component, such as a binary or multicomponent copolymer with vinyl ketone, vinyl ether, vinyl pyrrolidone, acrylamide, ethylene, butadiene, isoprene, chloroprene, etc. Among these, styrene polymers and copolymers containing the same as main components are preferred. The molecular weight of these polymers (C) is preferably 5,000 to 200,000. These (meth)acrylic acid ester polymers and styrene polymers can be produced by bulk polymerization, solution polymerization, emulsion polymerization, or suspension polymerization. Also, these (meta)
The acrylic ester polymer and the styrene polymer can also be used in combination. These polymers (C) are modified olefin polymers.
(A), or a polymer composition consisting of a modified olefin polymer (A) and an unmodified olefin polymer (B)
The amount is 2 to 50 parts by weight per 100 parts by weight. If the amount is less than 2 parts by weight, the effect of improving adhesion will be small, and if the amount is
Even if the amount is greater than 50 parts by weight, no more significant effect can be expected. Another active ingredient (D) in the adhesive resin composition of the present invention is No. 1 of the periodic table of elements.
The compound is a metal compound selected from oxides, hydroxides, phosphates, carbonates, and carboxylates of metals of the above group, and is preferably insoluble or sparingly soluble in water. Among these metal compounds, magnesium oxide, magnesium hydroxide, zinc oxide, zinc phosphate, aluminum oxide, aluminum hydroxide, aluminum phosphate, aluminum tripolyphosphate, and aluminum p-tert-butylbenzoate are particularly preferably used. Ru. Furthermore, these metal compounds are fine powders with a median diameter of 10 μm or less. Here, the adhesion improving effect of the present invention is due to the above component (C),
This effect is significantly exhibited by an appropriate combination with component (D). In this case, the amount of component (D) added should be the same as the above-mentioned modified olefin polymer (A) or polymer composition.
It is 0.01 to 10 parts by weight per 100 parts by weight. Further, in this case, especially when a metal oxide, hydroxide or phosphate is used in combination with an aromatic carboxylate, the adhesive strength is dramatically improved. The adhesive resin composition of the present invention can be produced by any method. For example, a method in which modified olefin polymer (A) is produced in advance and other components are added to it all at once; component (D) is added when producing modified olefin polymer (A), and then Method of adding modified olefin polymer (B) and component (C); Prepare a polymer composition mixture of polymer (A) and polymer (B) in advance and add components (C) and (D) to it. Adding method: Alternatively, make a master batch consisting of a part of polymer (B) and components (C) and (D), and add polymer (A) and polymer to this.
It can be produced by adding the remainder of (B); further, when producing polymer (A), components (C) and (D) are added, and then polymer (B) is added. Among these methods, particularly in the present invention, the polymer (A) is produced in advance, and then the polymer (B), the component (C) and
Recommended methods include adding (D) all at once, or adding components (C) and (D) as a masterbatch using polymer (A) or polymer (B). In this case, the composition is produced using a melt kneader such as an extruder, Banbury mixer, roll, or kneader. The melt index of the adhesive resin composition finally obtained in this way is preferably in the range of 0.1 to 100. In addition, this composition is powder,
It can take any shape depending on the purpose of use, such as pellets, sheets, films, fibrous materials, net-like materials, cloth-like materials, and tubular materials. The adhesive resin composition of the present invention can be widely used as a coating agent, binder, lamination adhesive, etc. for various base materials such as metals, various inorganic materials, and various polymeric materials. Among these, it is particularly effective as a metal coating agent and a lamination adhesive. The metal material, which is one of the above-mentioned base materials, is a single substance selected from metals of groups I-B, , , and of the periodic table, or an alloy containing these as one component. Among these, particularly preferred metals are aluminum, iron, nickel, cobalt, chromium, zinc, titanium, tin, gold, silver, copper, etc., or alloys of these metals, such as carbon steel, stainless steel, brass, bronze, and duralumin. and iron surface-treated products such as galvanized iron and tinplate. In order to effectively carry out the present invention, organic solvents such as petroleum benzine, toluene, xylene, acetone, trichloroethane, methylene chloride, etc. It is desirable to clean it using a disinfectant or the like. Further, the treatment can also be carried out by blasting treatment such as sandblasting or shotblasting, alkali treatment, phosphate treatment, chromate treatment, or a combination of these various treatment methods. Furthermore, if necessary, the surface can be treated with various primers such as epoxy resin, urethane resin, low molecular weight polybutadiene, etc. However, since the adhesive resin composition of the present invention itself has easy adhesion properties, it can be used to form coatings and laminates that are extremely strong and have excellent durable adhesion, even without special primer treatment. is obtained. Examples of inorganic base materials include glass, ceramics, asbestos, slate, gypsum, stone, and various other materials such as calcium carbonate, talc, alumina, silica, mica, boron nitride, zirconia, carbon, silicon carbide, and potassium titanate. natural or synthetic inorganic materials. The polymer compounds used as one of the above base materials include, for example, polyethylene, ethylene-vinyl acetate copolymer and its saponified product, ethylene-propylene copolymer, ethylene-(meth)acrylic acid copolymer and its saponified product. Metal salt, ethylene-(meth)
Ethylene copolymers and polyethylene derivatives such as acrylic acid ester copolymers and chlorinated polyethylene; polypropylene and propylene copolymers;
Polybutene-1; polystyrene, impact-resistant polystyrene, styrene-acrylonitrile copolymer,
ABS resin and other styrenic copolymers; polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, and other vinyl chloride copolymers; polyvinylidene chloride and vinylidene chloride copolymers; polyacrylonitrile and acrylonitrile copolymers; Methyl methacrylate and methyl methacrylate copolymers; poly(meth)acrylic esters and (meth)acrylic ester copolymers; natural rubber and polybutadiene, chloroprene, styrene-butadiene random or block copolymers, styrene- Synthetic rubber such as acrylonitrile copolymer; cellulose and cellulose derivatives and cellulose products such as cellophane, acetyl cellulose, and paper; nylon 6, nylon 66, nylon 11
polyamides such as; polyesters such as polyethylene terephthalate, alkyd resins, bisphenol A-terephthalic acid copolymers; polyethers such as polyoxymethylene and polyphenylene oxide; polycarbonates; other polyimides, polysulfones, polyketones, polyurethanes,
These are various natural or synthetic polymer compounds such as diallyl phthalate resin, epoxy resin, melamine resin, phenolic resin, and urea resin. Natural or synthetic polymer composite materials such as glass fiber reinforced resin, wood, bamboo, and leather can also be used. Furthermore, these base materials can be used as a mixture if necessary. Furthermore, in order to further improve the adhesion, if necessary, these substrates may be surface-treated by a general method such as corona treatment, ozone treatment, or anchor coating treatment. The above various base materials include powder, granular, film, sheet, fibrous, linear, rod-shaped, lump, cloth, net-shaped, tubular, spherical, container-shaped, etc. Primary processed products or secondary or higher processed products of various shapes, such as complex structures, are used. Also,
Two or more of these base materials can be used in any combination. By using the adhesive resin composition of the present invention and applying known processing techniques, various composite materials such as coatings, laminates, and reinforced resins having excellent adhesiveness can be manufactured. For example, in the production of coatings and laminates, fluid immersion method, electrostatic coating method,
Powder coating methods such as thermal spraying methods, solution coating methods, extrusion coating methods, dry lamination methods, heat pressure bonding methods,
Insert molding methods and combinations of these methods are applied depending on the purpose. Furthermore, filler-reinforced resins, fiber-reinforced resins, and the like can be manufactured by extrusion molding, injection molding, and the like. Additionally, antioxidants, heat stabilizers, light stabilizers, nucleating agents, lubricants, antistatic agents, inorganic or organic fillers, and inorganic or organic fillers may be added to the adhesive resin composition of the present invention, if necessary. Colorants, rust preventives, crosslinking agents,
Various additives such as foaming agents, lubricants, plasticizers, fluorescent agents, surface smoothing agents, and surface gloss improvers can be added during the manufacturing process of the resin composition of the present invention or in subsequent processing steps. The present invention will be explained below with reference to Examples, but the present invention is not limited thereto. The various measured values shown in the present invention are values obtained by the following methods. (1) Melt index Compliant with JIS K-7210 or K-6730, 2.16Kg
under a load of 230℃ for propylene polymers,
In the case of ethylene polymers, measurements were made at 190°C. The unit of measurement value is g/10min. (2) Content of unsaturated carboxylic acid or its anhydride in modified polymer The modified polymer was purified by dissolving it in heated xylene and precipitating with acetone, and was determined by alkaline titration. (3) Median diameter of metal compound Measured using a light transmission particle size distribution analyzer using ethyl alcohol as a medium. The median diameter is a value expressed as the 50% particle diameter of the cumulative particle size distribution curve. (4) Adhesive strength with steel plate 1 After degreasing a 150 x 70 x 3.2 mm grit-blasted steel plate with trichloroethane, it was heated to 160°C.
Or preheat to 180℃. On the other hand, a press sheet with a thickness of 0.3 mm was made from the adhesive resin composition, and this was laminated with a low-density polyethylene sheet (melt index 0.2) with a thickness of 2 mm.
After preheating to .degree. C., it was lightly pasted onto the above-mentioned preheated steel plate using a roller, and after 1 second had elapsed, it was put into water. Slits were made in this laminated board at 1 cm width intervals, at a temperature of 23°C and a tensile speed of 10 mm/min.
The 180° peel strength was measured. Part 2 After degreasing a 0.2 mm thick steel plate with trichloroethane and then treating it with an aqueous chromic acid solution, an adhesive resin composition with a thickness of 0.1 mm was interposed between the steel plates, and the temperature was 180°C and 10 Kg/cm ² A test piece with a width of 10 mm was made from this laminated plate, which was pressed for 2 minutes at a temperature of 23°C and a tensile speed of 200 mm/min.
The 90° peel strength was determined. As for durability, adhesive strength was measured after heating in an air oven at 100°C for 2000 hours. (5) Adhesive strength to aluminum After degreasing an aluminum plate with a thickness of 0.3 mm with a mixed solvent of acetone and toluene, an adhesive resin composition with a thickness of 0.1 mm was interposed between the aluminum plates. / ^cm2 for 2 minutes.
Hereinafter, the 90° peel strength was measured using the same method as in item (4) above. (6) Adhesive strength to polyamide or saponified ethylene-vinyl acetate copolymer (EVA) 0.3 mm thick nylon 6 (Toray, Rayfan)
T-1401) or saponified EVA (EVAL EF-E, manufactured by Kuraray), an adhesive resin composition with a thickness of 0.1 mm is interposed, and the adhesive resin composition is pressed for 2 minutes at 250°C and 10 kg/cm ² to bond them together. Ta. Hereinafter, the 90° peel strength was measured using the same method as in item (4) above. Example 1 Maleic anhydride content 2.5 mmol/100 g polymer graft-modified with maleic anhydride,
100 parts by weight of modified high-density polyethylene pellets with a density of 0.958 and a melt index of 2.7, molecular weight
70000 beaded polymethyl methacrylate 10 parts by weight, median particle size 2.7 μm and iodine adsorption amount 50
A mixture consisting of 3 parts by weight of magnesium oxide powder of mg・I/g・MgO was processed using a 100 mmφ twin screw extruder.
The mixture was kneaded at a temperature of 180° C. and an average residence time of 5 minutes to obtain composition pellets with a melt index of 1.4. The adhesion test results for this composition are shown in Table 1. Example 2 The modified high-density polyethylene used in Example 1 was
Composition pellets with a melt index of 3.7 were obtained according to the formulation and method of Example 1, except that 60 parts by weight of high-density polyethylene powder with a density of 0.960 and a melt index of 8 was added. The adhesion test results for this composition are shown in Table 1. Example 3 Melt index was obtained by the method of Example 2, except that 0.3 parts by weight of p-tert-butylbenzoic acid aluminum salt with a median diameter of 0.3 μm was added instead of magnesium oxide in the formulation of Example 2.
A composition pellet of 3.9 was obtained. The adhesion test results for this composition are shown in Table 1. Example 4 In the formulation of Example 2, additional p
A composition pellet having a melt index of 3.4 was obtained by the method of Example 2, except that 0.3 parts by weight of -tert-butylbenzoic acid aluminum salt was added. The adhesion test results for this composition are shown in Table 1. Comparative Examples 1 to 5 Using the same raw materials as Examples 1 to 4, the first
Composition pellets were obtained by the method of Example 1 except that the formulation shown in the table was used. The adhesion test results for this composition are shown in Table 1. Example 5 Maleic anhydride content 2.2 mmol/100 g polymer graft-modified with maleic anhydride,
20 parts by weight of modified ethylene-vinyl acetate polymer pellets with a vinyl acetate content of 10% by weight and a melt index of 6.4, 80 parts by weight of an ethylene-vinyl acetate copolymer with a vinyl acetate content of 5% by weight and a melt index of 5, molecular weight Example 1 A mixture consisting of 15 parts by weight of polystyrene pellets having a particle size of 25,000 and 4 parts by weight of magnesium hydroxide powder having a median diameter of 3.4 μm was prepared.
The mixture was kneaded at 160° C. using the same extruder as above to obtain composition pellets with a melt index of 4.2. The adhesion test results for this composition are shown in Table 1. Example 6 Composition pellets with a melt index of 4.3 were obtained by the method of Example 5, except that 4 parts by weight of tertiary zinc phosphate with a median diameter of 3.6 μm was added instead of magnesium hydroxide. Ta. The adhesion test results for this composition are shown in Table 1. Comparative Examples 6-7 Example 5 except that the same raw materials as in Examples 5 and 6 were used, and the formulations shown in Table 1 were used.
Composition pellets were obtained by the method described above. The adhesion test results for this composition are shown in Table 1. Example 7 Acrylic acid content 110 mmol/100 g polymer,
30 parts by weight of ethylene-acrylic acid direct copolymer with a melt index of 7, density 0.957, 70 parts by weight of high-density polyethylene with a melt index of 4, molecular weight
Extrusion using a mixture consisting of 5 parts by weight of polymethyl methacrylate having a molecular weight of 50,000, 5 parts by weight of polystyrene having a molecular weight of 25,000, an iodine adsorption amount of 45 mg·I/g·MgO, and 2 parts by weight of magnesium oxide having a median diameter of 2.5 μm was used in Example 1. The mixture was kneaded using a machine at 180°C to obtain composition pellets with a melt index of 4.3. The adhesion test results for this composition are shown in Table 1. Example 8 In the compounding recipe of Example 7, p
-tert-butylbenzoic acid aluminum salt powder 0.3
A composition pellet having a melt index of 4.1 was obtained by the method of Example 7, except that part by weight was added. The adhesion test results for this composition are shown in Table 1. Comparative Examples 9 and 10 Composition pellets were obtained by the method of Example 7, except that the same raw materials as in Examples 7 and 8 were used, and the formulations shown in Table 1 were used. The adhesion test results for this composition are shown in Table 1. From the results shown in Table 1 above, it can be seen that the adhesive resin composition of the present invention has much better adhesiveness than each of the Examples and the corresponding Comparative Examples. In particular, the compositions of Examples 2 to 4, that is, the blend compositions of modified high-density polyethylene and unmodified high-density polyethylene, exhibit very excellent adhesion to metals. Furthermore, among these examples, those in which magnesium oxide and p-tert-butylbenzoic acid aluminum salt were used in combination as the metal compound showed even more excellent adhesiveness. Example 9 A propylene-ethylene block copolymer graft-modified with maleic anhydride by a melt-kneading method using an extruder, and the maleic anhydride content was
3.2 mmol/100g polymer, melt index
27, modified polymer with die swell 1.87 (melt index of polymer before modification 2, die swell
1.53, intrinsic viscosity of crystalline polypropylene part 1.5,
Intrinsic viscosity of ethylene-propylene copolymer part: 5.3,
Crystalline propylene part/ethylene-propylene copolymer part weight ratio 70/30 and ethylene content of ethylene-propylene copolymer part 50% by weight) 30 parts by weight, the above-mentioned unmodified propylene-ethylene block copolymer powder 70 parts by weight, 10 parts by weight of polymethyl methacrylate with a molecular weight of 70,000 and an iodine adsorption amount of 50
A mixture of mg·I/g·MgO and 2 parts by weight of magnesium oxide powder with a median diameter of 2.7 μm was kneaded at 230°C using the extruder used in Example 1 to obtain composition pellets with a melt index of 4.5. . Example 10 A composition with a melt index of 4.3 was prepared by the method of Example 9, except that 0.3 parts by weight of p-tert-butylbenzoic acid aluminum salt with a median diameter of 0.3 μm was further added to the formulation of Example 9. Obtained pellets. Comparative Examples 11 and 12 The same raw materials as in Examples 9 and 10 were used, except that the formulations shown in Table 2 were used, respectively.
Composition pellets were obtained by the method described above. Examples 11-12 and Comparative Examples 13-14 Using the same raw materials as Examples 1-4, the second
Composition pellets were obtained by the method of Example 1 except for the formulation shown in the table. Example 13 Maleic anhydride content 2.3 mmol/100 g polymer graft-modified with maleic anhydride, density
30 parts by weight of modified low-density polyethylene with a melt index of 0.938 and 0.8, 70 parts by weight of linear low-density polyethylene with a density of 0.938 and a melt index of 4, and 10 parts by weight of the polymethyl methacrylate used in Example 9, respectively.
A mixture of parts by weight and 2 parts by weight of magnesium oxide was kneaded at 180°C in the extruder used in Example 1,
A composition pellet was obtained. Example 14 In addition to the formulation of Example 13, p-
Composition pellets were obtained by the method of Example 13, except that 0.3 parts by weight of tert-butylbenzoic acid aluminum salt was added. Comparative Examples 15 and 16 Composition pellets were obtained by the method of Example 13, except that the same raw materials as in Examples 13 and 14 were used, and the formulations shown in Table 2 were used. Example 15 40 parts by weight of modified high-density polyethylene graft-modified with hymic anhydride content 1.9 mmol/100 g polymer, density 0.957, melt index 3.6, high density 0.960, melt index 8 50 parts by weight of density polyethylene,
Mooney viscosity (100℃) 45, 10 parts by weight of ethylene-propylene copolymer rubber with 50% ethylene content, 40 parts by weight of styrene with 60% methacrylic acid content, methacrylic acid-styrene copolymer with molecular weight 22000. A mixture of 10 parts by weight and 2 parts by weight of tertiary zinc phosphate having a median diameter of 3.7 μm was kneaded in a Banbury mixer at 120 to 160° C. for 7 minutes, and then passed through an extruder to obtain composition pellets. Example 16 In addition to the formulation of Example 15, p-
Composition pellets were obtained by the method of Example 15, except that 0.3 parts by weight of tert-butylbenzoic acid aluminum salt was added. Comparative Examples 17 and 18 Composition pellets were obtained by the method of Example 15, except that the same raw materials as in Examples 15 and 16 were used, and the formulations shown in Table 2 were used. Above, Examples 9 to 16
Table 2 shows the results of examining the durable adhesion to metal of the compositions obtained in Comparative Examples 11 to 18. These results show that the composition of the present invention has excellent initial adhesion to metal as well as durable adhesion. Further, among these examples, those in which magnesium oxide or tertiary zinc phosphate and p-tert-butylbenzoic acid aluminum salt are used together as the metal compound have particularly excellent adhesive properties.

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Claims (1)

[Claims] 1 A modified olefinic polymer (A) containing an unsaturated carboxylic acid or its anhydride, or the olefinic polymer (A) and an unmodified olefinic polymer (B)
100 parts by weight of a polymer composition consisting of 2 to 50 parts by weight of a (meth)acrylic acid ester polymer and/or styrene polymer (C), and a median diameter of 10μ
Metal compounds (D) selected from the oxides, hydroxides, phosphates, carbonates and carboxylates of metals of groups 1, 2, of the periodic table of the following elements:
An adhesive resin composition comprising 0.01 to 10 parts by weight.