JPH03166283A - Adhesive resin and composite material - Google Patents

Abstract

PURPOSE:To obtain an adhesive resin suitable for plastic, metal, paper, wood, inorganic material, etc., by adding an unsaturated carboxylic acid (anhydride) and an organic peroxide to a resin composition of e.g. ethylene/alpha-olefin copolymer and subjecting the resin to graft-modification reaction. CONSTITUTION:The objective adhesive resin is produced by compounding (A) 100 pts.wt. of a resin composition composed of (i) 20-60 pts.wt. of a straight- chain ethylene/alpha-olefin copolymer having a density of >=0.915g/ml, (ii) 10-50 pts.wt. of a straight-chain ethylene/alpha-olefin copolymer having a density of <=0.910g/ml and (iii) 20-60 pts.wt. of an ethylene/ethyl acrylate copolymer having an ethyl acrylate content of 22-50wt.%, (B) 0.01-3.0 pts.wt. of an unsaturated carboxylic acid (anhydride) and (C) 0.001-1.0 pt.wt. of an organic peroxide and subjecting the mixture to graft-modification reaction. The adhesive resin is especially effective in firmly bonding the same or different kinds of hardly adhesive materials such as vinyl chloride resin, vinylidene chloride resin, iron, Al, PE and magnesium hydroxide.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to adhesive resins with excellent adhesive properties for plastics, metals, paper, wood, inorganic materials, etc., and composites or assemblies bonded with the resins. It is. More specifically, adhesive resins that can adhere well to difficult-to-adhere vinyl chloride resins, vinylidene chloride resins, iron, aluminum, polyethylene, magnesium hydroxide, etc., even if they are of the same or different types, and laminates bonded with the resins. , relates to composites or compositions such as multilayer pipes.

Conventional technology Modified resins made by grafting unsaturated carboxylic acids or their acid anhydrides onto low-pressure low-density polyethylene (LLDPE), high-density polyethylene (HDPE), ethylene-vinyl acetate copolymer (EVA), etc., have a high resistance to metals. has moderate adhesion, but it has poor adhesion to inorganic substances such as aluminum hydroxide, magnesium hydroxide, calcium carbonate, silica, and talc, or to plastics such as polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, polyester, and polycarbonate. It has the disadvantage of being defective. For this reason, for example, a laminated composite in which the above-mentioned modified resin is interposed between metal foil and plastic has insufficient adhesion strength between the layers. Some have the drawback of being brittle and having poor impact resistance.

In addition, it is known that acid-modified resins of ethylene-di-methyl acrylate copolymer with an ethyl acrylate content of less than 20% are used for adhesion between polyethylene and metals ("Kobunshi Proceedings"). ”, Vo1.36, No.l
ISp-759-765), which does not have sufficient adhesive strength.

Also, the ethyl acrylate content is 22-501! It has been proposed to make a composite or composite by adhering or mixing % of acid-modified resin of ethylene-ethyl acrylate copolymer with metal, inorganic material, or different plastic (Japanese Patent Application Laid-Open No. 61293247). ), this composite shows better adhesion than ethylene-ethyl acrylate copolymer with an ethyl acrylate content of less than 20%, but with the advancement of the times, the required performance in each technical field has become stricter, There is a need for polyolefin adhesive resins that exhibit excellent adhesive properties and other properties.

In particular, in gas barrier layer laminated films for food packaging, polyvinylidene chloride, polyvinyl chloride, polyamide, polyester, ethylene-vinyl alcohol copolymer, aluminum foil, etc. are used as the gas barrier layer, and these materials can be mixed with other base materials. It is used by laminating it with a polyolefin resin that has good thermal weldability and self-sealing properties, but adhesion between the gas barrier layer and the polyolefin resin layer is difficult due to the difference in SP value between the two, so various polymer compositions are used. , Special J:
Acid-modified polymer compositions have been proposed, but they are not fully satisfactory, and many of the general-purpose polyvinyl chloride and polyvinylidene chloride resins contain plasticizers. Adhesion was inevitably impaired due to bleeding.

Other adhesives are used to coat the surface of steel pipes with polyethylene to protect them from corrosion, but this also lacks sufficient adhesion, impact resistance, low-temperature properties, etc., and is not strong enough. Adhesive resin was requested.

In addition, in order to obtain a halogen-free resin composite that does not generate toxic gas when burned, inorganic substances such as magnesium hydroxide and aluminum hydroxide are added in large amounts to 65 t parts per 100 parts by weight of the polyolefin resin composite. Some additives clear flame retardant standards, but the impact resistance of these molded products decreases! Therefore, there has been a strong demand for adhesive resins that can firmly bond inorganic materials and polyolefin resins.

On the other hand, a composite made of a modified polyolefin obtained by grafting an unsaturated carboxylic acid or an acid anhydride thereof of a linear ethylene-a-ole7ine copolymer having a density of 0.91 h/tJ2 or less (JP-A-62-2003) 182582) and linear ethylene-α with a density of 0.91h/+iQ or more.
- An adhesive composition comprising an acid modified product of an ole7yne copolymer with an unsaturated carboxylic acid or its acid anhydride and an acid of an ethylene-ethyl acrylate copolymer or its acid anhydride (
JP-A No. 59-71350) has also been proposed,
None of these methods fully meet the above requirements.

Problems to be Solved by the Invention The present invention overcomes the drawbacks of conventional adhesive resins, and provides adhesive resins that have high adhesive properties and other properties such as mechanical strength. It is made with the purpose of providing.

Means for Solving the Problems The present inventors have conducted various studies in order to develop adhesive resins having the above-mentioned preferable properties. Ethylene-ethyl acrylate copolymer with high ethyl acrylate content, which has superior adhesion than acid-modified acrylate copolymers, linear ethylene-α-ole7yne copolymer with a specified density or higher, specified density We have developed acid-modified products such as the linear ethylene-σ-ole7yne copolymer shown below, but we discovered that we could achieve this goal by integrating these technologies, and based on this knowledge, we As a result, the present invention has been completed.

That is, in the present invention, (A) (B) the density is 0.9159
/One or more linear ethylene-α-olefin copolymers 2
0 to 60 parts by weight, (mouth) 10 to 50 parts by weight of a linear ethylene-a-ole7ine copolymer having a density of 0.91 h/mQ or less, and (c) ethylene having an ethyl acrylate content of 22 to 50% by weight. -Ethyl acrylate copolymer 20-6
(B) unsaturated carboxylic acid or its acid anhydride to 100 parts by weight of the resin composition consisting of 0.0 parts by weight. Ol~3.0 parts by weight and (C) organic peroxide 0.001~1.0! It is added with the "IT" moiety and subjected to graft modification to provide a certain adhesive resin.

The present invention will be explained in detail below.

In the present invention, the composition (A) of the resin composition (A)
and (mouth), each with a density of 0.9159/mf
f or more and 0.910 g/l (2 or less), each linear ethylene-σ-olefin copolymer contains a transition metal compound of Groups tV to ■ of the periodic table and an organic metal of Groups I to ■ of the periodic table. It is produced by gas-phase, low-pressure copolymerization using a catalyst obtained by combining with other compounds.

More specifically, in the present invention, the resin composite (A)
The density is 0-915, which is used as the structural component (a) of
The linear ethylene-σ-ole7yne copolymer having a particle size of g/+mQ or more can be prepared using a known method, that is, using a transition metal compound (compounds such as titanium or panadium) as a main catalyst and an organometallic compound (e.g. organoaluminum, etc.) as a co-catalyst. Ethylene and σ-ole7ine are polymerized under medium or low pressure in the presence of a Ziegler catalyst consisting of a carrier (such as magnesium chloride, etc.), a carrier (such as an oxide of silicon, titanium, magnesium, etc.), a chromium-based catalyst, etc. can get.

The a-ole7ynes used in this case include propylene, butene-t, hexene-L octene-11-decene-L
etc. are preferred.

Various methods are used for this polymerization, such as slurry polymerization, gas phase polymerization, and high-temperature solution polymerization, and a particularly desirable method is the gas phase method disclosed in JP-A-54-154488. Yes, and has been commercialized by the applicant.

According to this gas phase process, the structure (a) is prepared by using a titanium-containing catalyst in a fluidized bed process at a pressure of less than 1000 psi in the gas phase, with a melt 7 low ratio of about 22 to 32, at least 90 A granular ethylene copolymer containing ethylene units equivalent to 500 mole % ethylene per lb titanium
In manufacturing with a productivity of 00 lb or more, ethylene and 1
species or two or more species of C, ~C. a-olefin monomers and the catalyst system in the presence of not more than 0.2 moles of hydrogen per mole of ethylene in a gas phase reaction zone at a temperature of about 30-115°C. the catalyst system comprises an activated precursor set having the formula MgX, where X is CQ, Br, and mixtures thereof) and at least one magnesium compound represented by the formula Ti(OR)aXb (wherein R is a C1 to C. aliphatic or aromatic hydrocarbon group or COR'( Here, R' is C I- C l 4
is an aliphatic or aromatic hydrocarbon group), and
has the above meaning, a is 0 or l, b is 2 to 4
and a+b is 3 or 4] and an alkyl ester of an aliphatic or aromatic carboxylic acid in which the titanium compound, the magnesium compound, and the precursor compound are soluble. , aliphatic ethers, cyclic ethers and aliphatic ketones, wherein the magnesium compounds, titanium compounds and electron donating compounds are dissolved in m%n% as defined below.
The formula MgmTiQ(OR)nXp(ED)q (wherein R and X are As described above, ED is the liquid organic electron donating compound, m is 0.5 to 56, n is 0 or l, and p is 6 to 56.
116, q is 2 to 85), and the precursor composition is mechanically mixed or compounded with at least one solid inert carrier, and the precursor composition is or before feeding it to the reaction zone,
10 to 4 per mole of titanium compound in the precursor composition
With 00 moles of activator compound adsorbed on the carrier, 5
Fully activated so that a solid dry catalyst composition is prepared below 0°C, or partially activated with an amount of activator compound not exceeding 10 moles per mole of titanium compound in the precursor composition. 10 to 400 per mole of titanium compound in the precursor mixture in the reaction zone after activation
molar of the activator compound, the activator compound has the formula A(1(R")cX'dHj, where X' is CQ or OR#', R" and R#
' may be the same or different 01-C. is a saturated hydrocarbon group, d is O~1.5, e is 0 or l, c+d
It is produced by a contact production method of an ethylene copolymer consisting of an organoaluminum compound represented by +j-3).

More specifically, in the present invention, a linear ethylene-σ-olefin copolymer having a density of 0.9109/II12 or less, which is used as the structure 1'R component (b) of the resin composition (A). The combination is carried out using a known method, that is, using a transition metal compound (compounds such as titanium or vanadium) as the main catalyst,
In the presence of an organometallic compound (e.g. organoaluminium, magnesium chloride, etc.) and a carrier (e.g. oxides of silicon, titanium, magnesium, etc.) as a cocatalyst, a Ziegler catalyst, a chromium-based catalyst, etc. are used to react ethylene and σ-ole7. It is obtained by polymerizing Yin in a specific ratio under medium or low pressure.

As the a-olefin used in this case, propylene, butene-11hexene-11octene-11decene-1, etc. are preferable.

Various methods are used for this polymerization, such as slurry polymerization, gas phase polymerization, and high-temperature solution polymerization, and a particularly desirable method is the gas phase method disclosed in JP-A-59-230011. Yes, and has been commercialized by the applicant.

According to this gas phase method, the above structure is carried out in a fluidized bed reaction zone at a temperature of 10 to 80°C and a pressure of 7.000 kPa.
At the following pressures: (a) 0.35: 1 ~ 8.0
: ethylene and at least one higher q-olefin having from 3 to 12 carbon atoms in a molar ratio of 1 higher a-olefin to ethylene; (b) at least 25 mol % of at least one diluent gas; The containing gas mixture has the formula MgmTi (OR) n is an aromatic hydrocarbon group), and X is CQ
, Br, I, and mixtures thereof, and ED is an alkyl ester of aliphatic or aromatic carboxylic acid, an aliphatic ether, in which the titanium compound and magnesium compound and the precursor composition are soluble. A liquid organic electron-donating compound selected from the group consisting of cyclic ethers and aliphatic ketones, where m is 0.5 to 56, n is 0,
1 or 2, p is 2 to 116, and q is 2 to 85]. With dilution, the formula Al2(R')cX'dHj (where X' is CQ or OR"' and R# and R#
′ may be the same or different. is a saturated hydrocarbon group, d is O-1.5, e is 0 or LC+d+
j-3), and the aluminum compound is completely activated with an organoaluminum compound represented by
It is produced by a continuous process for producing ethylene copolymers, which comprises using the ethylene copolymer in an amount within the range of .

In the present invention, the ethylene-ethyl acrylate copolymer used as the component (c) of the resin composition (A) contains 22 to 50% by weight of ethyl acrylate units, for example, ethylene and ethyl acrylate. It is obtained by radical polymerization under high pressure, and usually has a Torto index (ASTM D 1238
1.00 to 300 is used.

If the ethyl acrylate unit content is less than 22% by weight, the resulting modified resin will have insufficient adhesion to other base materials, and if it exceeds 50% by weight, the heat resistance and mechanical The properties are deteriorated, and when the film is formed into a film, blocking between the films becomes large, which reduces workability, which is undesirable.

In the present invention, the content ratio of the three types of ethylene copolymers constituting the resin composition (A), components (a), (b), and (c), has a density of 0.915 g/m4. 20 to 60 parts by weight of the above linear ethylene-σ-ole7yne copolymer,
Density is 0.9109/l (linear ethylene of 2 or less - σ
- 10 to 50 parts by weight of the ole7yne copolymer and 20 to 60 parts by weight of the ethylene-ethyl acrylate copolymer.

If the content of the linear ethylene-σ-olefin copolymer with a density of 0.915 g/II12 or more is less than 20 parts by weight, the mechanical strength of the adhesive layer will be weak, and the
If the weight part is exceeded, mechanical strength, hot tack properties, heat seal strength at high temperatures, etc. will be improved, but the amount of resin that contributes to other adhesive properties will be reduced, resulting in poor adhesion, impact peel resistance, low temperature properties, and low temperature properties. This is undesirable because heat-sealing properties, contaminant heat-sealing properties, etc. deteriorate.

In addition, if the content of the linear ethylene-a-olefin copolymer with a density of 0.91 h/mα or less is less than 10 parts by weight, impact peelability, low-temperature properties, low-temperature heat-sealability, contaminant heat-sealability, etc. The properties and impact removability will deteriorate.
Moreover, if it exceeds 50 parts by weight, the density, which is responsible for mechanical properties, will be 0.
．． In addition to reducing the amount of linear ethylene-a-olefin copolymer of 915 g/+++Q or more, the content of ethylene-ethyl acrylate copolymer with high EA content, which exhibits the best adhesiveness with other substrates, is also reduced. This is relatively low and undesirable.

Furthermore, if the content of the ethylene-ethyl acrylate copolymer in the structure Flt (c) is less than 20 parts by weight, the adhesion to other base materials, especially the adhesion to polyolefin resins, will deteriorate. , and when it exceeds 60 parts by weight, the density is 0.915 g/ which mainly plays a role in mechanical strength and hot tack properties.
The amount of ethylene-σ-olefin copolymer of 112 or more and the density, which plays a role in impact peeling resistance, low temperature properties, low temperature heat sealability, contaminant heat sealability, impact resistance, etc., are 0.910.
The amount of the ethylene-α-olefin copolymer having a ratio of 9/yxQ or less becomes relatively small, which is undesirable.

In the present invention, examples of the unsaturated carboxylic acid or its acid anhydride used as the additive (B) include acrylic acid, methacrylic acid, maleic acid, succinic acid, phthalic acid, itaconic acid, methyl acrylate, and acrylic acid. methyl methacrylate, fumaric acid, crotonic acid, citraconic acid, maleic anhydride, phenyl maleic anhydride, itaconic anhydride, bromic maleic anhydride, aryl maleic acid imide, alkyl maleic acid imide, citraconic anhydride, Chloromaleic anhydride, hexahydrophthalic acid, tetrahydrophthalic acid, benzenetricarboxylic acid, benzenetetracarboxylic acid, Himic acid, Himic anhydride, tetrachlorophthalic acid, dodecenylsuccinic acid, cinnamic acid, oleic acid, linoleic acid, linolenic acid , linseed oil fatty acids, dehydrated castor oil fatty acids, among others, maleic acid, maleic anhydride, phthalic anhydride, acrylic acid,
Himic acid anhydride is preferred.

In the present invention, the organic peroxide used as the additive (C) has a decomposition temperature of 100 to 22
0°C, that is, the half-life temperature for 10 minutes is 10O~2
Those having a temperature of 20° C. are preferable, and examples of such materials include the following.

However, the value in parentheses is the decomposition temperature (°C).

Succinic acid peroxide (110), penzoyl peroxide (110), t-butylberoxy-2-ethylhexanoate (113), p-'7-lobenzoyl peroxide (115), t-butylperoxyisobutyrate (115) ), t-butylperoxyisoglobyl carbonate (135), t-butylperoxylaurate (140), 2,5-dimethynole-2,5-di(
Bezoinoleperoxy)hexane (140), t-butylperoxyacetate (l40), di(-butyldiperoxy7thaleate (140), t-butylperoxymaleic acid (140), cyclohexanone peroxide (145), [-Butylberoxybenzoe-}
(145), dicumylberoxy (150), 2.5
-dimethyl-2,5-di(t-butylperoxy)hexane (155), t-butylcumyl peroxide (15)
5), t-butyl hydroperoxide (158), di-t-butyl peroxide (160), 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3 (
170), diisopropinolebenzene hydroperoxide (170), p-menthanehydroperoxide (
180), 2,5-dimethylhexane-2,5-dihydroperoxide (213).

The adhesive resin of the present invention has an additive content (B) of 0.01 to 3.0 parts by weight and an additive content (C) of 0.001 to 1.0 parts by weight per 100 parts by weight of the resin composition (A). Add parts by weight,
It is made by graft modification.

If the amount of the unsaturated carboxylic acid or acid anhydride added as the additive component (B) is less than 0.01 part by weight, the adhesiveness will be insufficient, and even if it is added in an amount greater than 3.0 parts by weight. The improvement in adhesion does not improve any further, which is undesirable because economic efficiency is impaired.

If the amount of organic peroxide added (C) is less than 0.001 part by weight, the graft reaction will not occur and adhesive properties will not be imparted, and if it exceeds 1 part by weight, ethylene-based This is undesirable because it causes crosslinking in the polymer and deteriorates the processing properties, and the gel tends to impair the surface properties and transparency of the film.

The graft modification is usually carried out at a reaction temperature of 120-300'O, preferably 170-220'C.

In this way, the adhesive resin of the present invention is obtained.

The adhesive resin of the present invention may optionally contain various additives conventionally used in adhesive resins, such as antioxidants, lubricants, adhesives, organic・Various inorganic pigments, UV inhibitors, dispersants, neutralizing agents,
Nucleating agents, crosslinking agents, flow improvers, dyes, flame retardants, antistatic agents, antifogging agents, antifog agents, rust preventives, antibacterial agents, and the like may be included.

The composite or composite material of the present invention includes the adhesive resin and
It is made of materials such as plastic, metal, wood, paper, and inorganic materials.

Plastics in such materials include, for example, polyethylene homopolymer, ethylene-a-ole7yne homopolymer, ethylene-propylene copolymer, propylene-butene-l copolymer produced by high-, medium-, and low-pressure processes. , copolymers mainly composed of propylene with other σ-olefins, polybutene-l1boly-4methyl pentene-l1ethylene-propylene-diene copolymers, ethylene-vinyl acetate copolymers, ethylene-ethyl acrylate copolymers Polymer, ethylene-acrylic acid copolymer, ethylene-glycidyl methacrylate copolymer, ethylene-maleic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-ethyl methacrylate copolymer, ABS resin, Vinyl chloride resin, vinylidene chloride resin, polystyrene, styrene-acrylonitrile copolymer, polymethyl methacrylate, styrene-methyl methacrylate-acrylonitrile copolymer, α-methylene-acrylonitrile copolymer,
a-methylstyrene-styrene-acrylic nitrile copolymer, methacrylic acid-butadiene-styrene resin, polyamide, polyester, polycarbonate, polyacetal, polyoxymethylene, polyphenylene oxide,
Acrylic acid resin, polyimide, regenerated cellulose, cellulose derivative, borisulfone, epoxy resin, allyl resin, unsaturated polyester, alkyd resin, polyamideimide, phenolic resin, amino resin, furan resin, vinyl ester resin, silicone resin, synthetic rubber, natural rubber,
Examples include natural resins.

Good adhesive strength cannot be obtained with other adhesive resins for such plastics.

When the adhesive resin of the present invention is used, good adhesive strength can be obtained especially for polyvinyl chloride containing plasticizers, polyvinylidene chloride, saponified products of ethylene-vinyl acetate, engineering plastics, etc. Good adhesive strength can also be obtained against.

Examples of the metal in the material include foils, sheets, rods, plates, wires, powders, fibers, whiskers, etc., such as iron, aluminum, copper, lead, and zinc.

Inorganic substances in the materials include carbon, boron, silicon carbide, alumina, silica, glass, potassium titanate, xonotlite, wollastonite, mica, sericite, talc, calcium carbonate, shirasu, magnesium sulfate, muscovite, and phlogovite. , asbestos, magnesium silicate, clay, bentonite, zeolite, attabulgite, pumice, slate, feldspar, wollastonite, tripolite, silica, calcium silicate, hydrotalcite, antimony trioxide, titanium dioxide, zinc oxide, carbonate Examples include powders of magnesium, barium sulfate, aluminum hydroxide, magnesium hydroxide, carbon black, etc., fibers, whiskers, foils, sheets, plates, flakes, wire-like articles, and shaped articles.

Examples of the composite body include those in the form of a laminate, a multilayer pipe, a wire and cable structure, an insert molding, a foam, etc. Among these, a laminate is particularly preferred.

Examples of this laminate include, for example, a laminate of adhesive resin and vinyl chloride resin, a steel pipe coated with polyethylene resin via adhesive resin, and preferably magnesium hydroxide coated with polyethylene resin via adhesive resin. Examples include steel pipes coated with kumikaimono dispersed in resin.

In order to produce the composite or assembly of the present invention, for example, the above-mentioned adhesive resin and plastic, metal, wood, paper,
Methods such as adhering or mixing materials such as inorganic substances in a molten state are used. There are no particular restrictions on the method of adhesion or mixing. For example, for adhesion, there are methods such as forming a film or sheet and bonding them under heat, laminating them outside the die, laminating them inside the die, extrusion coating, etc. Any known method can be used.

Effects of the Invention The present invention provides a crystalline linear ethylene-α-olefin copolymer having a density of 0.915 g/1112 or more, a density of 0.910
Since the adhesive resin is an acid-modified mixture of a low-crystalline linear ethylene-a-olefin copolymer with a weight ratio of less than α and an ethylene-ethyl acrylate copolymer with a high ethyl acrylate content, it can be used for various base materials. It has excellent adhesion to, tear strength, tensile strength, impact strength, puncture strength, haze, etc., so it can be used as various laminated films or sheets, laminated bottles, laminated containers, laminated pipes, etc. Food packaging materials, stretch films, wrap films, heat-shrinkable films, carpet packing, shielding layers for wires and cables, shielding materials such as electromagnetic wave shielding materials, power cable shielding layers and conductive water tape, female fuel materials, automobiles. Suitable for use in parts, semiconductive layers, carrying tools, toys, etc.

EXAMPLES Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples in any way.

Example l Linear ethylene-butene-l copolymer (NUCG-5211,
(manufactured by Nippon Unica Co., Ltd.) 20 parts by weight, density 0.906 g/m
l12% M I O. 8 linear ethylene protein
Copolymer (DFDA-1137, manufactured by Nippon Unicar Co., Ltd.) 40 parts by weight, ethyl acrylate content 35% by weight
, density 0.95 g/1112, ethylene-ethyl acrylate copolymer with M 1 2.0, maleic anhydride 0.
5 parts by weight, 1.1-bis(t-butylperoxy)
-3.5.5- 0.1 part by weight of trimethylcyclohexane (Perhexa 3M, manufactured by NOF Corporation) was mixed in a Henschel mixer at room temperature, and the mixture was fed to a vented extruder with a diameter of 50 mm and extruded at 200 °C. , cylindrical pellets were produced.

The modified resin pellets thus obtained were heated at 165°C and 100ky/crs using a heat press machine.
A sheet having a thickness of 0.5++n, a length of 150 mm, and a width of 180 mm was prepared under conditions of , 2 minutes. This sheet and iron, copper,
Sheets or foils of aluminum, polyvinyl chloride, polycarbonate, saponified ethylene-vinyl acetate copolymer, high-pressure polyethylene, LLDPESVLDPE, etc., were laminated as both outer layers of the intermediate layer of the modified resin sheet, at a temperature of 180°C and a pressure of 30hg/ C1 for 2 minutes to obtain each three-layer laminate. The thickness of metal foil is 0
．． 2mm, the thickness of the plastic sheet is 2. OIIIl
I used the one from

The above three-layer laminate was cut into test pieces with a width of 10 mm and a length of 150 mm, and tested using an Instron universal tensile tester according to JIS K6.
A peel test was conducted in accordance with 854 to measure the peel strength between the modified resin and various metals or plastics. however,
The pulling speed is 90° peel of 100ms+/min. The evaluation results are shown in Table 1. Further, in order to evaluate various performances of the modified resin film, the modified resin film obtained by the above method was made by an inflation method using air cooling using the following equipment and processing conditions.

Extrusion device: Inflatable 3-in processing device manufactured by Plako Co., Ltd. Diameter 40 mm, L/D-28 Annular die: l = 150 mi + die gap -1.00 Cooling device: Single lip straight and conical collar Discharge amount: 4 5 & 9/hr Die temperature: 180 Blow ratio: 2.5 7 Film thickness: 20 μ Table 1 shows the results of measuring the tear strength, tensile strength, impact strength, puncture strength, and haze of the produced film. ．． Examples 2 to 9, Comparative Examples 1-13 By the same method as Example 1 except that the resin, unsaturated carboxylic acid or its acid anhydride, and organic peroxide types and amounts used in Example 1 were changed. We conducted an experiment. Good results were obtained in the examples.

Nell book 2 Ne3 book 4 Ne5 book 6 book 7 book 8 book 9 Density: 0.921g/gift 12 MI: 1.0 Ethylene-butene-l copolymer manufactured by Nippon Unicar Density: 0.92 h/mi2 MI: 2 .7 Ethylene-hexene-l copolymer manufactured by Nippon Unicar Density: 0.9209/11112 M I: 1. O
Ethylene-octene-l copolymer density: 0.906 g/mi2 M I : 0.8 manufactured by Idemitsu Petroleum Ethylene-butene-l copolymer density manufactured by Nippon Unicar: 0.910 g/*a M I = 1.0 Nippon Unicar Ethylene-butene-l-hexene-l copolymer density: 0.949/112 M I: 2.5 Ethylene-ethyl acrylate copolymer (75% by weight) (25% by weight) manufactured by Nippon Unicar Density: 0. 95g/IIIα M I: 2.5 Nippon Unicar ethylene-ethyl acrylate copolymer (6
(5% by weight) (35% by weight) Density: 0.923g/ rtrQ M I : 2.4
Nippon Unicar Ethylene homopolymer density: 0.93 g/aa MI: 6 Nippon Unicar Ethylene-ethyl acrylate copolymer (82% by weight) (18% by weight) Density: 094 g/aa MI: 2.5 Ethylene-vinyl acetate copolymer (82% by weight) (18% by weight) manufactured by Nippon Unicar Ill density: 0.96 g/mQM I: 35 Ethylene-vinyl acetate copolymer (65% by weight) (35% by weight) manufactured by Nippon Unicar * l2 Same as $8 113 Same as book 14 Same as 4 *15 Explained in example l 16 ASTM DI'J22 Eretondorf book 17
ASTM D882 Table 8 Falling ball impact ASTM Dl709 This l9 film is stretched 30% and has an embossed tip (
Tip R O. with radius 0.5+am. Strength book 20 when breaking through (5 fights) ASTM 01003

Claims (1)

[Scope of Claims] 1 (A) (a) 20 to 60 parts by weight of a linear ethylene-α-olefin copolymer having a density of 0.915 g/ml or more, (b) a density of 0.910 g/ml or less 100 parts by weight of a resin composition comprising 10 to 50 parts by weight of a linear ethylene-α-olefin copolymer of (B) 0.01 to 3.0 parts by weight of an unsaturated carboxylic acid or its acid anhydride and (C)
An adhesive resin that is graft-modified by adding 0.001 to 1.0 parts by weight of an organic peroxide. 2. A composite comprising the adhesive resin according to claim 1 and at least one material selected from plastic, metal, paper, wood, and inorganic materials. 3. The composite according to claim 2, wherein the composite form is a laminate. 4. The composite according to claim 3, which is a laminate of the adhesive resin according to claim 1 and a vinyl chloride resin. 5. A steel pipe coated with polyethylene resin via the adhesive resin according to claim 1. 6. A steel pipe coated with a composition in which magnesium hydroxide is dispersed in a polyethylene resin via the adhesive resin according to claim 1. 7. A composition comprising the adhesive resin according to claim 1 and at least one material selected from plastic, metal, paper, wood, and inorganic materials.