JPS5986651A - Polyolefin adhesive resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which can be bonded to metal at a low temp. in a short time and has excellent permanent adhesion, consisting of an unsaturated carboxylic acid (anhydride)-modified olefin polymer, and unmodified olefin polymer, a specified resin and a metallic compd. CONSTITUTION:2-98pts.wt. modified olefin polymer having an unsaturated carboxylic acid (anhydride) content of 0.002-30wt% and an MI of 0.5-20g/ 10min such as maleic anhydride-graft modified high-density PE and 98-10pts.wt. unmodified olefin polymer having an MI of 0.1-100g/10min such as high-density PE are blended together to obtain a polymer compsn. (A) having an unsaturated carboxylic acid (anhydride) content of 0.001wt% or above. 2-50pts.wt. resin selected from cyclized rubber, petroleum resin, rosin, polyterpene, cumarone/ indene resin and ketone resin and 0-10pts.wt. metallic compd. selected from oxides, hydroxides, phosphates, carbonates and carboxylates of Groups II to VIIImetals are blended with 100pts.wt. component A.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an adhesive resin composition, and more particularly to a resin composition with excellent adhesive properties, the main component of which is an olefinic polymer modified with an unsaturated carboxylic acid or its anhydride. It is something.

As is well known, polyolefins such as polyethylene and polypropylene have various excellent physical and chemical properties, mechanical properties, and moldability, and together with their low cost, they are used in many industries. Widely used in the field. However, since these polyolefins are nonpolar, they have poor adhesion to different materials such as metals, glass, and polar polymer 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 adhesiveness by introducing polar groups, for example, by copolymerizing ethylene and acrylic acid, or by graft modification of polyolefins with acrylic acid or maleic anhydride.

Furthermore, various polyolefin compositions and methods for producing the same have been proposed for the purpose of further improving adhesiveness with 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 a polyolefin and graft-modifying it while melting (Japanese Patent Publication No. 51-48195, Japanese Unexamined Patent Publication No. 49-198) 98484
No. 50-10887), a composition prepared by adding a metal oxide such as magnesium oxide to a polyolefin graft-modified with acrylic acid or maleic anhydride (Japanese Patent Application Laid-open No. 51-28544, JP-A-51-28544, Kaisho 52-12
1059), compositions of polypropylene graft-modified with unsaturated carboxylic anhydride and ethylene polymers (JP-A-52-14684, JP-A-52-26)
No. 548, JP-A No. 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 No. 56-21850); Publication No. 54-90846), and compositions of ethylene copolymers containing polar groups such as carboxyl groups and styrene polymers (Japanese Patent Application Laid-open No. 54-90846).
Many polyolefin adhesive resin compositions are known, such as Japanese Patent Laid-Open No. 1-184782 and Japanese Patent Application Laid-open No. 148039/1983. 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 such as wood-coated steel pipes, sandwich steel plates, and aluminum laminated sheathed cables for communications, in order to reduce processing costs through energy saving and high-speed processing, methods are being developed at lower temperatures and in shorter times. There is a strong demand for resins that can be easily bonded. However, many conventional adhesive resin compositions have insufficient adhesive strength, and even if initial adhesive strength is good, durable adhesiveness is poor. Furthermore, as mentioned above, from the viewpoint of low-temperature, short-term adhesiveness, no resin has yet been found that has satisfactory adhesive strength.

In view of the current situation, the inventors of the present invention conducted extensive studies in order to obtain a resin composition that easily adheres to various substrates, especially metals, at low temperatures and in a short time, and that also has excellent durable adhesive properties. We have discovered an adhesive resin composition that is significantly superior to conventional products, leading to the present invention.

That is, the present invention comprises (1) 2 to 98 parts by weight of a modified olefin polymer containing 0.002 to 80% by weight of an unsaturated carboxylic acid or its anhydride, and (b) 98 to 10 parts by weight of an unmodified olefin polymer. 100 parts by weight of a polymer composition comprising at least 0.001% by weight of an unsaturated carboxylic acid or its anhydride, (0) mU of cyclized rubber, petroleum! , rosin, polyterpene, coumaron-indene resin and ketone resin2~
50 parts, and oxides, hydroxides, phosphates, carbonates (5), and carboxylates of metal rods from group Ⅰ to number 1 of the periodic table of the elements added as necessary. Metal compounds selected from 0
It is a polyolefin adhesive resin composition consisting of ~10 parts by weight.

Here, the adhesive polyethylene resin composition of the present invention has the feature that it not only has easy adhesion as described above, but also extremely strong and durable adhesion irrespective of large fluctuations in usage environmental conditions. Because it has such properties, the adhesive resin composition of the present invention can be used, for example, as a coating for steel pipes, as an intermediate adhesive for sandwich laminates such as steel plates, stainless steel plates, and aluminum plates, and as an intermediate adhesive for polyamides, polyurethanes, polyesters, ethylene-vinyl It can be effectively used as a coating agent, binder, and lamination adhesive for various inorganic and organic substrates including metals, such as lamination adhesives such as alcohol copolymers, polyethylene, polypropylene, and ethylene-vinyl acetate copolymers. Materials manufactured in this way are used for vehicle parts, ship parts, aircraft parts, civil engineering and construction materials,
(6) It can be widely used as electrical parts, furniture, office supplies, packaging materials, etc.

The present invention will be explained in detail below.

The olefin polymer containing a carboxylic acid group or a carboxylic acid anhydride group, 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. , include the following:

For example, acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, hymic acid, bicyclo(2
,2,2) oct-5-ene-2,8-dicarboxylic acid,
4-Methylcyclohex-4-ene-1,2 dicarboxylic acid, 1,2,8.4.5,8.9゜10-o')tavidronaphthalene-2,8-dicarboxylic acid, bicyclo(2,
2,1) Oct-7-ene-2,8,5,6-tetracarboxylic acid, 7-oxabicyclo(2,2,1) but-
Direct copolymers of unsaturated carboxylic acids such as 5-ene-2,8 dicarboxylic acid and their anhydrides with ethylene, or these in addition to methyl (meth)acrylate, (meth)
Ethyl acrylate, n-butyl (meth)acrylate, (
Unsaturated carboxylic acid derivatives such as 8th-butyl meth)acrylate, acrylamide, maleic acid mono- or diester, vinyl esters such as vinyl acetate and vinyl propionate, propylene, butene-1,4-methylpentene-
1. Those obtained by copolymerizing copolymerizable monomers such as unsaturated hydrocarbons such as styrene, α-methylstyrene, and chlorostyrene and derivatives thereof may be mentioned. These polymers can be produced by a known vacuum 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 olefin polymers.

Examples of the olefin polymer that is the base of this graft copolymer include low density polyethylene, linear low density polyethylene, light density polyethylene, crystalline or non-grade polypropylene, crystalline or non-grade propylene-ethylene random copolymer, etc. Polymer, crystalline or amorphous propylene-ethylene block copolymer, ethylene-propylene-
Non-conjugated 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-methyl(meth)acrylate copolymer, ethylene-( Ethyl meth)acrylate copolymer, ethylene-butyl(meth)acrylate copolymer, ethylene-(meth)acrylic acid or its partial metal salt copolymer, ethylene-(meth)acrylic acid-(meth)acrylic acid Various olefin homopolymers and copolymers can be used, such as ester copolymers, ethylene-vinyl alcohol copolymers, ethylene-vinyl acetate-vinyl alcohol copolymers, and ethylene-styrene copolymers. Moreover, two or more types of these olefin polymers can also be used in combination. The above-mentioned graft copolymer may be prepared by a known method (9), for example, a melt mixing method using an extruder, Banbury mixer, Nigu, roll, etc. in the presence or absence of a radical initiator.1 Toluene, xylene , a heterogeneous slurry method using a solution using a solvent such as chlorobenzene and a non-solvent such as ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, or dioxane, or a modification method using a powder system. The content of unsaturated carboxylic acid or its anhydride in the modified olefin polymer produced by these methods is 0.002 to 80
% by weight.

Further, the melt index of the modified olefin polymer is preferably in the range of 0.5 to 20. If the value is less than 0°5, short-term adhesiveness tends to deteriorate.

In the present invention, the above-mentioned modified olefin polymer and unmodified olefin polymer (b) are separated by weight/(B)=2
A polymer composition consisting of: /98 to 90/10 is used as the main component of the adhesive composition.

(lO) As this unmodified olefin polymer, one selected from among the olefin polymers that are the base of the above-mentioned graft copolymer is used, for example. The melt index of the polymer is preferably from 0.1 to 100.

The content of unsaturated carboxylic acid or its anhydride in the polymer composition must be at least o, ooi% by weight. If it is less than 0.001% by weight, adhesiveness will be low.

The resin used as one component of the adhesive resin composition of the present invention (Q is natural rubber, butadiene rubber, isoprene rubber,
Cyclized rubber obtained by cyclizing chloroprene rubber, isoprene from petroleum distillate, piperylene, 2-methylbutene-1,
Petroleum resins manufactured from 2-methylbutene-2, styrene, vinyltoluene, α-methylstyrene, indene, etc., rosin, polyterpene, coumaron-indene resins, ketone resins manufactured from cyclohexanone, acetophenone, etc., and their hydrides. , a modified product such as a maleide. The amount of these resins added is in the range of 2 to 50 parts by weight per 100 parts by weight of the mixture of the modified olefin polymer and the unmodified olefin polymer. If this amount is less than 2 parts by weight, the effect of improving adhesion will be small, while if it is more than 50 parts by weight, there will be no more significant effect on adhesion.

Among the metal compound powders which may be optionally added as another active ingredient of the adhesive resin composition of the present invention, particularly preferably used are oxides and hydroxides of magnesium, zinc and aluminum. , carbonates, phosphates and carboxylates. The amount of these metal compounds added is in the range of 0 to 10 parts by weight per 100 parts by weight of the mixture (b) of the modified olefin polymer and the unmodified olefin polymer. 0.
Adding 0.01 parts by weight or more has a great effect. Specific examples of metal compounds that are preferably used include magnesium oxide, magnesium hydroxide, magnesium carbonate, zinc oxide,
Examples include zinc phosphate, aluminum oxide, aluminum tripolyphosphate, and aromatic carboxylates such as aluminum P-tart-butylbenzoate and magnesium P-tert-butylbenzoate. Among these, especially metal oxides, hydroxides or phosphates
．． 1 to 1 part of ON and 0.01 to 2 parts of aromatic carboxylate
When used in combination in weight parts, the effect of improving adhesion is extremely large.

The adhesive resin composition of the present invention is generally produced by melt-kneading using an extruder, Banbury mixer, kneader, or roll nutrer.

The composition thus produced can take any form depending on the purpose of use, such as powder, pellet, film, fibrous material, net-like material, cloth-like material, or tubular material. In addition, various other island molecule compounds can also be added to the adhesive resin composition of the present invention, if necessary.

The adhesive resin composition of the present invention can be widely used as a coating agent, a binder, a lamination adhesive, etc. for various (18) substrates 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 materials that are one of the above base materials are listed in the periodic table I-B.
It is a simple substance selected from metals of the It, Ill, ■, ■, and ■ groups, or an alloy containing these as one component. Among these, particularly suitable metals include aluminum, iron, nickel, cobalt, chromium, zinc, titanium, tin, gold, silver, copper, carbon steel, stainless steel, brass, bronze, etc.
These are alloys of these metals such as duralumin, and surface-treated products of iron such as galvanized iron and tinplate. In order to effectively carry out the present invention, petroleum benzene,
It is preferable to use an organic solvent such as toluene, xylene, acetone, trichloroethane, methylene chloride, or a surfactant for cleaning. Also, sandblasting,
The treatment can also be carried out by blasting such as shot blasting, alkali treatment, phosphate treatment, chromium (14) salt 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 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. can get.

Examples of inorganic base materials include glass, ceramics, asbestos, slate, gypsum, stone, calcium carbonate, talc, alumina, silica, mica, boron nitride,
Examples include various natural or synthetic inorganic materials such as zirconia, carbon, silicon carbide, and potassium titanate.

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 salts, ethylene-(meth)acrylate copolymers, chlorinated polyethylene, etc. Ethylene copolymers and polyethylene derivatives Polypropylene and propylene copolymers; Polybutene-1; Polystyrene, impact-resistant polystyrene, styrene-acrylonitrile copolymers Coalescence, A, BS resin and other styrenic copolymers; polyvinyl chloride, vinyl chloride-vinyl acetate copolymers and other vinylized vinyl copolymers; polyvinylidene chloride and vinylidene chloride copolymers; polyacrylonitrile and acrylonitrile-based Copolymers; Polymethyl methacrylate and methyl methacrylate copolymers; Poly(meth)acrylic esters and (meth)acrylic ester copolymers; Natural rubber and polybutadiene, chloroprene, styrene-butadiene random or block Synthetic rubbers such as copolymers and styrene-acrylonitrile copolymers; cellulose derivatives and cellulose products such as tenlulose and cellophane, acetyl cellulose, and paper; polyamides such as nylon 6, nylon 66, and nylon 11; polyethylene terephthalate, alkyds! 11! , polyesters such as bisphenol A-terephthalic acid copolymers; polyethers such as polyoxymethylene and polyphenylene oxide; polycarbonates; other polyimides, polysulfones, polyketones, polyurethanes, diallyl phthalate resins, epoxy resins, melamine resins, phenolic resins, urea resins etc., various natural or synthetic polymer compounds. 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 various base materials mentioned above include powder, granular, film, sheet, fibrous, linear, rod-shaped, lump, cloth, net-shaped, tubular, spherical, and container-shaped materials (17). Primary processed products or secondary or higher processed products of various shapes, such as objects and other complex structures, are used. Further, two or more types 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 strong resins having excellent adhesiveness can be manufactured. For example, in the production of coated bodies and laminates, fluid coating methods, electrostatic coating methods, powder coating methods such as thermal spraying methods, solution coating methods, extrusion coating methods, dry lamination methods, thermocompression bonding methods, insert molding methods, Furthermore, combinations of these may be 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.

In addition, for the adhesive resin composition of the present invention, an antioxidant, a heat stabilizer, a light stabilizer, a lubricant, an antistatic agent,
Various additives such as inorganic or organic fillers, inorganic or organic colorants, rust preventives, crosslinking agents, foaming agents, plasticizers, fluorescent agents, surface smoothing agents, surface gloss improvers, etc. It can be added during the manufacturing process of the resin composition of the present invention or during the subsequent processing process.

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) Based on melt index JIS K-7210 or NI-6780,
2.2 for propylene polymer under a load of 16V4
In the case of 80°C mono-ethylene polymer, the measurement was performed at 190°C. The unit of measurement value is g/10mln.

(2) Content of unsaturated carboxylic acid or unsaturated carboxylic acid anhydride in modified polymer The modified polymer was dissolved in heated xylene and purified by precipitation with acetone, and the content was determined by alkaline titration.

(8) Median diameter of metal compound Measured using a light transmission particle size distribution analyzer using ethyl alcohol as a medium. The median diameter is 5 of the integrated particle size distribution curve.
This value is expressed as 0% particle size.

(4) Adhesive strength with steel plate 1 After degreasing a 150 x 70 x 8.2 inch grid-blasted steel plate with trichloroethane, it was heated to 140°C or
Preheat to 60°C.

On the other hand, a press sheet with a thickness of 0.3 cm was made from the adhesive resin composition, and this was then attached to a polyethylene sheet with a thickness of 2 ml (
After preheating to 280°C, they were laminated onto the above preheated steel plate using a roller, and after 1 second, they were poured into water. Slits with a width of 1cW were made in this laminated board at 1cW intervals, and the temperature was 28°C and the tensile speed was 10m/min.
6 Peel strength was measured.

Part 2 A steel plate with a thickness of 0.2 yem was degreased with trichloroethane, then treated with an aqueous solution of chromic acid, and then an adhesive resin composition with a thickness of 0.1 cm was interposed between the steel plates.
℃ and 10 Kf/cd for 2 minutes to bond them together.

A test piece with a width of 10++ m was prepared from this laminate, and a test piece was prepared at a temperature of 2
The 90° peel strength was determined at 8°C1 tensile rate of 200 w/min. 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 0.8 wm with a mixed solvent of acetone and toluene, an adhesive resin composition with a thickness of 0.1 m is interposed between the aluminum plates, 1
Pressed at 90'C% 10Kf/ffl 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) Nylon-6 with a thickness of 0.8 ttm (Reifan T-1401 manufactured by Toshi) or saponified EVA (21) ( Made by Kuraray, EVAL EF-E) with a thickness of 0.1
tts adhesive resin composition, 250°C, 1
They were bonded together by pressing at 4/d for 2 minutes. Hereinafter, the 90° peel strength was measured using the same method as in item (4) above.

Example 1-1 Density 0.959 containing 0.85% by weight of maleic anhydride
and graft-modified high-density polyethylene 40 with a melt index of 2.6, a density of 0.960, and a graft-modified high-density polyethylene 6 with a melt index of 7.5.
0 positioning part and cyclized rubber (Seikoka handmade, Thermolite K
) 10 parts by weight of the mixture was kneaded in a 58 Ω twin-screw extruder at a temperature of 180° C. and an average residence time of 2 minutes to obtain composition pellets.

Examples 1-2 to 1-6 In Example 1-1, in place of the cyclized rubber, petroleum resin (Takkiroll 5000, manufactured by Sumitomo Chemical Co., Ltd.), rosin (Gum rosin type, manufactured by Arayo Chemical Co., Ltd.), and polyterpene (An J.
Example 1-1 was repeated except that Jltlfll, YS (22) resin), coumaron-indene resin (manufactured by Nippon Steel Chemical Co., Ltd.) and ketone resin (manufactured by Honshu Chemical Co., Ltd., acetophenone type) were used.

Comparative Examples 1-1 to 1-6 Examples 1-1 and 1-6, respectively, except that the unmodified polyolefin was not used and the amount of modified polyolefin was 100 parts by weight in Examples 1-1 to 1-6. repeated.

Comparative Example 2-1 Example 1-1 was repeated except that no resin component 0 was added.

Example 2-1 The mixture of Example 1-4 had a median diameter of 2.7 μm and an adsorption amount of 80111? I/9Mf10O) oxidation v
Examples 1-4 were repeated except that 4 parts by weight of gnesium was added.

Example 2-2 4 parts by weight of magnesium oxide used in Example 2-1 and P − with a median diameter of 0.3 μm were added to the mixture of Example 1-4.
Example 1-1 was repeated except that 0.8 parts by weight of tert-butylbenzoic acid aluminum salt was added.

Examples 2-3 to 2-4 Ketone resin (manufactured by Honshu Chemical, cyclohexanone type) instead of the polyterpene used in Examples 2-1 to 2-2
Examples 2-1 and 2-2 were repeated, respectively, except that .

Example 8-1 7'l lylic acid content 12% by weight, melt index 7
．． A mixture of 20 parts by weight of the ethylene-acrylic acid copolymer No. 8, 80 parts by weight of the high-density polyethylene used in Example 1-1, and 10 parts by weight of R rubber was kneaded by the method of Example 1-1, Composition pellets were obtained.

Comparative Example 8-1 Example 3-1 was repeated except that no cyclized rubber was added in Example 8-1.

Above, Examples 1-1-1-6.2-1 to 2-4 and 8
-1 and Comparative Examples 1-1 to 1-6.2-1 and 8-
Table 1 shows the results of examining the composition obtained in 1 and its adhesion to various substrates. These results show that the composition of the present invention has excellent adhesion to various substrates. Among these, especially Examples 2-1 to
As shown in No. 2-4, those to which a metal compound was added, especially those to which a combination of magnesium oxide and P-tert-butylbenzoic acid aluminum salt were added, showed significantly excellent adhesion.

Example 4-1 Maleic anhydride content 0.25% by weight, density 0.962
．． 20 parts by weight of graft-modified high-density polyethylene with a melt index of 2.4, density 0.960. A mixture of 80 parts by weight of high-density polyethylene having a melt index of 7.6 and 15 parts by weight of the polyterpene used in Example 1-4 was kneaded by the method of Example 1-1 to obtain composition pellets.

(25) Example 4-2 Maleic anhydride content 0.24% by weight, density 0.937
, 20 parts by weight of graft-modified linear low-density polyethylene with a melt index of 0.8, 80 parts by weight of linear low-density polyethylene with a density of 0.988 and a melt index of 4.7, and 15 parts by weight of the polyterpene used in Example 1-4. The mixture was kneaded by the method of Example 1-1 to obtain composition pellets.

Example 4-3 Maleic anhydride content 0.21% by weight, density 0, 924
, 20 parts by weight of graft-modified low-density polyethylene with a melt index of 4.2, a density of 0.922. A mixture of 80 parts by weight of low density polyethylene having a melt index of 2.0 and 15 parts by weight of the polyterpene used in Example 1-4 was kneaded by the method of Example 1-1 to obtain composition pellets.

Example 4-4 Maleic anhydride content 0.24 wt%, acetic acid (26) hinyl containing filO wt%, melt index 5.1
A mixture of 20 parts by weight of the graft-modified ethylene-hinyl acetate copolymer, 80 parts by weight of low-density polyethylene having a density of 0.922 and a melt index of 2.0, and 15N parts of the polyterpene used in Examples 1-4 was prepared in Example 1. The mixture was kneaded by the method of -1 to obtain composition pellets.

Comparative Examples 4-1 to 4-4 Examples 4-1 to 4-4 were repeated except that no polyterpene was added.

Example 5-1 Maleic anhydride content 0.82% by weight, ethylene content 1
[12.5% by weight, 20 parts by weight of graft-modified propylene-ethylene block copolymer with melt index 17, ethylene content 12.5% by weight, melt index 2.2 nophlopylene-ethylene block copolymer 80
Parts by weight, 5 parts by weight of the coumaron-indene resin used in Example 1-5, median diameter 2.7μ, iodine adsorption amount 50
A mixture of 4 parts by weight of magnesium oxide with (1), I/g, and MpO was kneaded by the method of Example 1-1 to obtain composition pellets.

Comparative Example 5-1 Except that the amount of the modified propylene-ethylene block copolymer used in Example 5-1 was 0.2 parts by weight and the amount of the propylene-ethylene block copolymer was 99.8 parts by weight. , Example 5-1 was repeated.

Comparative Example 5-2 The amount of graft-modified propylene-ethylene block copolymer with maleic anhydride content o, oooa wt%, ethylene content 12.5 wt%, melt index 15 was 1
Example 5-1 was repeated except that 00 parts by weight and no unmodified propylene-ethylene block copolymer was added.

Example 6-1 A mixture of 20 parts by weight of the modified propylene-ethylene block copolymer used in Example 5-1, 80 parts by weight of crystalline polypropylene with a melt index of 1.8, and 5 parts by weight of polyterpene was prepared in Example 1-1. The mixture was kneaded by the method described above to obtain composition pellets.

Example 6-2 Example 6-1 was repeated except that 2 parts by weight of the magnesium oxide used in Example 5-1 was added to the mixture of Example 6-1.

Example 6-8 2 parts by weight of magnesium oxide used in Example 5-1 and P-t used in Example 2-2 were added to the mixture of Example 6-1.
Example 6-1 was repeated except that 0.2 parts by weight of ert-butylbenzoic acid aluminum salt was added.

Comparative Example 6-1 Example 6-1 was repeated except that no polyterpene was added.

Example 7-1 Maleic anhydride-containing ffi 0.17% by weight, ethyl (2
9) 40 parts by weight of graft-modified crystalline propylene-ethylene random copolymer with a syn content of 4.1% by weight and a melt index of 25, crystalline propylene-ethylene with an ethylene content of 5.2% by weight and a melt index of 2.6. A mixture of 60 parts by weight of the random copolymer, 5 parts by weight of the polyterpene used in Example 1-4, and the magnesium oxide used in Example 5-1 was kneaded by the method of Example 1-1 to obtain composition pellets. Ta.

Comparative Example 7-1 Example 7-1 was repeated except that no polyterpene was added.

Above, Examples 4-1 to 4-4.5-1.6-1 to 6-8
and 7-1 and comparative examples 4-1 to 4-4.5-1 to
Table 2 shows the results of examining the adhesion between the compositions obtained in 5-2.6-1 and 7-1 and steel plates. These results show that the adhesive resin composition of the present invention not only has good initial adhesion to steel plates but also excellent durable adhesion (80). Furthermore, as shown in Examples 6-2 and 6-8, the effect when a specific metal compound is added is particularly remarkable.

Continuing from page 1 0 Inventor Setsuo Moriyo 1-1 Oe-cho, Niihama-shi Resident Kagaku Kogyo Co., Ltd. Amendment (method) % formula % l Incident indication 1980 Patent Junso 197276 No. 2, Invention Name of Polyolefin Thread Adhesive Resin Composition 3, Relationship to the Amendment Case Address of Patent Applicant 5-15 Kitahama, Higashi-ku, Osaka Name (
20'J Sumitomo Chemical Co., Ltd. Representative Sat
Takeshi 4, Agent

Claims (1)

[Claims] (5) Unsaturated carboxylic acid or its anhydride
Modified olefin polymer 2-98 containing ~30% by weight
Parts by weight and 03) Unmodified olefin polymer 98-1
(C) cyclic rubber, petroleum resin, rosin, polyterpene; , 2 to 50 parts by weight of a resin selected from coumaron-indene resins and ketone resins, and oxides of metals from Groups 1 to 1 of the periodic table with zero elements added as necessary, and water. Metal compounds selected from oxides, phosphates, carbonates and carboxylates 0-
A polyolefin adhesive resin composition consisting of 10 parts by weight.