JPH0198677A - Adhesive resin composition and laminate thereof on metal - Google Patents

Abstract

PURPOSE:To provide a resin compsn. having excellent brine resistance and adhesion, by blending a polyolefin resin contg. a modified olefin polymer with a small amt. of a hydroxyalkylphenylbenzotriazole compd. CONSTITUTION:100pts.wt. polyolefin resin (A) contg. at least 0.1wt.% olefin polymer modified with an unsatd. carboxylic acid and/or its anhydride [e.g., ethylene or propylene polymer modified with maleic acid (anhydride)] is blended with 0.1-1.0pt.wt. hydroxyalkylphenylbenzotriazole (B) of the formula (wherein R is 1-8C alkyl) [e.g., 2(2-hydroxy-5-methylphenyl)-2H-benzotriazole] to prepare an adhesive resin compsn. The compd. B is readily available, easily blendable, capable of improving the brine resistance of the compsn. even when blended therein in a small amt. for the compsn. to exhibit excellent adhesion and persistance thereof even when brought into contact with a brine or corrosive soln. Thus, the adhesive resin compsn. can be suitably used for coated steel pipes (particularly to be used under sea water or buried in coil), coated electric wires, and coated steel plates.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention provides a resin composition with excellent salt water resistance and adhesive properties, and a method for bonding a metal or primer-treated metal primer layer using the resin composition as an adhesive layer. The present invention relates to a laminate formed by combining In more detail, underground pipes, rivers or seabeds used for transporting gas, water, petroleum, etc.
The present invention relates to adhesive resin compositions and laminates thereof suitable for plastic-coated metal plates and composite metal plates used as various industrial materials, including glass-coated metal pipes such as PE brine.

[Conventional technology]

J?, which has good chemical stability, is used for the protection (corrosion prevention) of metals such as conventional steel pipes and steel plates. A method of coating the surface with a lyolefin resin has been adopted and is used in various industrial fields as plastic coated steel pipes and coated steel sheets.

Needless to say, polyolefin resins are chemically non-polar, so even if you try to heat and melt them to adhere to a metal molded object such as a steel pipe, they will easily peel off after cooling and solidifying, so they cannot be used with non-polar resins such as maleic anhydride. A coating is performed in which an olefinic resin modified with a saturated carboxylic acid or its derivative is interposed.

However, it is known that when it comes into contact with liquids containing electrolytes such as seawater or saline, or corrosive aqueous solutions in buried soil, the adhesive strength significantly decreases, causing a serious problem in practical use. Therefore, in order to solve this problem, a thermosetting epoxy resin (so-called primer) was interposed between the metal molded body and the modified olefin resin layer (adhesive layer). -115239
No. 57-827, No. 56-14223, Japanese Patent Publication No. 56-53476), epoxy resins containing condensed cynic acid compounds (Japanese Patent Application Laid-open No. 55-140552), aluminum oxide powder and amine-based resins. An attempt was made to interpose a specific epoxy resin containing a curing agent (Japanese Unexamined Patent Publication No. 57-159866), and a modified polyolefin resin with sic acid salt (Japanese Patent Publication No. 54-18297), which has a tendency to ionize.
Large metal powder (Japanese Patent Publication No. 58-13585), specific divalent metal compounds containing rhodan (Japanese Patent Publication No. 59-29Sho.
607, No. 60-2330), etc. have been proposed.

[Problem that the invention seeks to solve]

However, although these primer treatments and compositions containing specific compounds can prevent a significant decrease in the adhesive strength of the garden to some extent, the adhesive strength is not satisfactory, and the long-term adhesive durability is not satisfactory. It is unsatisfactory.

In addition, in general, a process is adopted in which a resin-based Zolimer is applied to improve salt water resistance, and this process is necessary in terms of equipment costs, as well as process control and material control. It's not something I'm satisfied with either.

In view of the above, the present invention is to obtain a resin composition that does not have these drawbacks (problems) and has excellent adhesive durability, and a laminate made by bonding the resin composition to metal. .

[Means for solving problems]

According to the present invention, these problems are solved by the following: An adhesive resin composition containing 0.1 to 1.0 parts by weight of a hydroxyalkylphenylbenzotriazole compound represented by formula (1), and a metal or primer treatment using the adhesive resin composition as an adhesive layer. This problem can be solved by a laminate made by laminating a metal primer layer and a metal primer layer. The present invention will be explained in detail below.

The polyolefin resin used in the present invention is an olefin polymer (hereinafter referred to as a "modified olefin polymer") modified with an "unsaturated carboxylic acid and/or its anhydride" (hereinafter referred to as a "carboxylic acid compound"). ) containing at least 0.1% by weight.

(4) Olefin resin The olefin resin used to produce the modified olefin polymer used in the present invention and the olefin resin used to produce the composition together with the modified olefin polymer include: Homopolymers of olefins having 2 to 6 carbon atoms, copolymers of two or more of these olefins, and one or more of these olefins as a main component (generally 50% by weight or more) with other double bonds Examples include copolymers with other monomers having the following.

Examples of olefins include ethylene, propylene, 1-butene, 1-hexene, 3-methyl-1-f-tene, 3-methyl-1-pentene and 4-methyl-1-pentene.

Other monomers include vinyl acetate, acrylic acid, alkyl acrylate, methacrylic acid, alkyl methacrylate, styrene, vinyl chloride, and acrylonitrile.

Among these olefin resins, ethylene homopolymers and copolymers containing ethylene as a main component (hereinafter referred to as "ethylene polymers"). Propylene homopolymers and copolymers mainly composed of propylene (hereinafter referred to as "propylene-based polymers"); 1-butene homopolymers and copolymers mainly composed of 1-butene (hereinafter referred to as "butene-based polymers") ``coalescence'') is preferred.

Ethylene polymers include ethylene homopolymers produced by any of the high-pressure method, medium-pressure method, and low-pressure method;
Copolymer of ethylene and α-olefin having 3 to 6 carbon atoms (e.g., propylene, 1-butene, 1-e-entene, 1-hexene, 4-methyl-1-pentene), ethylene and carbon number are at most 8 alkadienes (e.g., 1,2-butadiene, 1j3-butadiene, 1.
4--1! copolymers with ethylene and other monomers (st, t#-1', vinyl acetate, vinyl alcohol, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate) Examples include copolymers with

In addition, as the propylene polymer, propylene homopolymer, propylene and ethylene, and/or the other α
-Random or block copolymers with olefins.

Furthermore, as the butene-based polymer, 1-butene homopolymer, ethylene with a copolymerization ratio of at most 10 molt with 1-butene, and/or other α-
Olefins (e.g. propylene, 4-methyl-1-
-e-entene, 1-hexene, 1-octene).

Furthermore, a mixture of the butene-based polymer and 50% by weight or less of other α-olefin polymers can be used.

Although there are no particular regulations regarding these olefin resins, the melt flow rate [for ethylene polymers,
Measured under conditions 4 according to JISK7210, below r
MFR (1) J], [for propylene polymers, measured under conditions 14 according to JIS K7210, hereinafter referred to as r MFR (2)] is a measure of the moldability, mechanical strength, etc. of the resulting composition. From the point, usually 0.01~100
y-710 minutes and 0.05 to 50? / 10 minutes is desirable, and the difference is 0.1 to 50 minutes. /10 minutes is suitable.

In the present invention, whether the modified olefin polymer described below is produced or a composition is produced together with the modified olefin polymer, the olefin resin used may be either one type or a combination of two or more. You may. Furthermore, in any of the above cases, the olefin resin alone may be used, or it may be used in combination with the nidistomer described below.

Typical examples of diystomers include copolymer elastomers of ethylene and α-olefins such as ethylene-propylene copolymer elastomers, ethylene-butene-1 copolymer elastomers, ethylene, α-olefins, and diene compounds (diene-based The copolymerization ratio of the compound is usually 10% by weight or less). Reinbutylene, polybutadiene rubber, syndiotactic rubber containing 90 or more 1,2-bonds and having a crystallinity of 10 to 40
Examples include 1,2-polybutadiene and butyl rubber.

Examples of diene compounds include ethylidene, dicyclopentadiene, and 1,4-hexadiene.

Regarding elastomers other than the ethylene-butene-1 copolymer disstomer, the molecular weight is not particularly specified, but the Mooney viscosity [■4. +4, (100℃)] is usually 5
~150, preferably between 10 and 100. In addition, for ethylene-butene-1 copolymer elastomer, the melt flow index (JIS K 7210
(measured under conditions 4) is generally 1 to 50i
P710 minutes, particularly preferably 2 to 25 iP/10 minutes.

As mentioned above, when producing a modified olefin polymer as described below, or when producing a composition together with the modified olefin polymer, the mixing ratio is not particularly specified when using a nidistomer. , usually at most 10 parts by weight per 100 parts by weight of the olefinic resin.
0 parts by weight, preferably 50 parts by weight or less, especially 30 parts by weight.
Parts by weight or less are preferred. If the mixing ratio of the elastomer to 100 parts by weight of the olefin resin exceeds 100 parts by weight, the moldability and heat resistance of the resulting composition will be poor.

Addition of these elastomers not only improves the adhesion of the composition, as is already known, but also has the effect of suitably adjusting the flow characteristics during melt coating.

However, the method for producing a modified olefin polymer The modified olefin polymer of the present invention is treated (modified) with a carboxylic acid compound in the presence of the olefin resin or the olefin resin and an elastomer radical initiator. It can be manufactured by

(1) Carboxylic acid compounds The carboxylic acid compounds used in the production of the modified olefin polymer are unsaturated carboxylic acids and their anhydrides. 12 or less, preferably 10 or less) and at least one carbon-carbon double bond and having at most 20 carbons (preferably).

(18 or less, preferably 15 or less) and has at least one carbon-carbon double bond.
Examples include phosphoric acid. Preferred representative examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid and 5-normenene-2,3-dicarboxylic acid. Examples of the anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, and 5-norrunene-2,3-dicarginic anhydride. Among these carboxylic acid compounds, maleic acid, 5-nor-2,3-dicarboxylic acid, maleic anhydride, and 5-nor? Runen-2
, 3-dicargenic acid anhydride is preferred.

(2) Radical initiator Also, as a radical initiator used for producing modified olefin polymers, the 1 minute half-life temperature is usually 1 minute.
A temperature of 00°C or higher is preferred, and a temperature of 110°C or higher is particularly preferred. Representative examples of the radical initiator include lafuroyl gum oxide, benzoyl gloss oxide, tertiary-butyl peroxybenzoate, dicumyl i'? -oxide, 2,5-dimethyl-2,5-di(
tertiary-butyl-oxy)hexane, di-tertiary-
Butirno J? -oxide and 2,5-dimethyl-2
,5-di(E-class-butyl-oxy)hexyne-3
Organic peroxides such as Two or more of these organic peroxides may be used in combination, if necessary.

(3) Usage ratio The usage ratio of the carboxylic acid compound and the radical initiator to 100 parts by weight of the total amount of the olefin resin or olefin resin and elastomer is as follows.

For carboxylic acid compounds, usually 0.01 to 5.0
It is preferably 0.02 to 3.0 parts by weight, particularly preferably 0.05 to 2.0 parts by weight.

If the proportion of the carboxylic acid compound used is less than 0.01 part by weight, the adhesiveness of the resulting modified olefin polymer will be insufficient. On the other hand, if it exceeds 5.0 parts by weight, the carboxylic acid compound may remain in the polymer or unreacted decomposition or crosslinking reactions may occur during the production of the modified olefin polymer. It is difficult to obtain a good modified olefin polymer.

In addition, for radical initiators, generally 0.001
~3.0 parts by weight, preferably 0.005 to 2.0 parts by weight, particularly preferably 0.01 to 1.0 parts by weight. If the proportion of the radical initiator used is less than 0.001 parts by weight,
Modification may be insufficient and unreacted carboxylic acid compounds may be mixed in the modified olefin polymer. On the other hand, 3
．． If it exceeds 0 parts by weight, it is not preferable because it causes excessive decomposition or stagnation reaction.

(4) Production of modified olefin polymer In producing the modified olefin polymer of the present invention,
The olefin resin, elastomer (if used), carboxylic acid compound, and radical initiator may be used alone or in combination of two or more.

In order to produce the modified olefin polymer of the present invention, any of various known production methods (eg, solution method, suspension method, melt method) can be employed.

Among these production methods, when producing a modified olefin polymer by a solution method, an olefin resin and an unsaturated carbonate are mixed in a nonpolar organic solvent. A modified olefin polymer can be obtained by adding phosphoric acid and/or its anhydride, further adding the above-mentioned radical initiator, and heating at a high temperature. At this time, the nonpolar organic solvents used are hexane, hebutane, benzene, toluene,
Mention may be made of xylene, chlorobenzene and tetrachloroethane. Furthermore, the treatment temperature is the temperature at which the olefin resin used is dissolved, and is generally 110 to 160.
℃, preferably 130 to 150℃.

In addition, when producing a modified olefin polymer by the suspension method, olefin resin and unsaturated carbon are mixed in a polar solvent (generally water). acid and/or its anhydride, and further added the above-mentioned radical initiator and reacted under high pressure.
It can be obtained by processing at a temperature of 00°C or higher.

Furthermore, when producing a modified olefin polymer by the melt method, a melt kneader (for example, an extruder, a Banbury mixer) used in the field of general synthetic resins is used.
It can be obtained by treating an olefinic resin, an unsaturated carboxylic acid and/or its anhydride, and the above-mentioned radical initiator while melt-kneading the mixture. The crosstalk temperature varies depending on the type of olefin resin and radical initiator used, but is in the temperature range from above the melting point of the olefin resin used to below 300°C. In the case of ethylene polymers, generally 12
0 to 280°C, and in the case of propylene polymers,
Generally it is 160-250 degreeC.

In order to produce modified olefin polymers using other modification methods, known methods may be applied.

(C) Hydroxylalkylphenylbenzotriazole compound Furthermore, the general formula of the hydroxylalkylphenylbenzotriazole compound used in the present invention is the following formula [
(Natsu) is a compound represented by the following formula].

A representative example of the hydroxylalkylphenylbenzotriazole compound represented by formula (1) is $11.2
-(2-hydroxyl-5-methyl-phenyl)-2H
-penztriazole, 2-(hydroxyl-5-fg
Examples thereof include tertiary--ff-ruphenyl)-2H-penzotriazole and 2-(2-hydroxyh-5-tertiary-7silufenyl)-2H-benzotriazole.

(6) Composition ratio The preolefin resin of the present invention contains at least 0.1 part by weight of the above-mentioned modified olefin polymer. That is, the preolefin resin may be a modified olefin polymer ["the elastomer modified with an unsaturated carboxylic acid and/or its anhydride"]
(hereinafter referred to as "modified nidistomer"), the same shall apply hereinafter], and is composed of this modified olefin polymer and the unmodified olefin resin.

The proportion of the modified olefin polymer in the preolefin resin is at least 0.11 parts by weight, preferably 1.0 parts by weight or more, and particularly preferably 5.0 parts by weight. If the proportion of the modified olefin polymer in the polyolefin resin is less than 0.1 parts by weight, the adhesion to metals will be insufficient, which is not preferable.

Further, the total content of monomer units of unsaturated carboxylic acid and/or its anhydride in the polyolefin resin is usually 0.001 to 1.4 molty, particularly 0.001 to 1.4 molty.
．． 01 to 1.0 molty is preferred.

Unsaturated carginic acid and/or in the polyolefin resin
If the total content of the monomer units of the anhydride is less than 06,001 molty, the resulting composition will not have sufficient adhesive strength. On the other hand, if it exceeds 1.4 molt,
Not only is no improvement in adhesive strength expected, but it is also unfavorable from an economic standpoint.

Furthermore, the composition ratio of the hydroxylalkylphenylbenzotriazole compound is the same as that of the polyolefin resin 1.
0.1 to 1.0 parts by weight, and 0.00 parts by weight.
2 to 1.0 parts by weight is desirable, and the difference is 0.3 to 0.8 parts by weight.
Parts by weight are preferred. If the composition ratio of 100 parts by weight of the hydroxylalkylphenylbenzotriazole compound is less than 0.1 part by weight, the effect of improving salt water resistance is poor.

On the other hand, even if it is blended in an amount exceeding 1.0 parts by weight, no further improvement effect can be obtained; in fact, excessive blending not only has a negative effect on the adhesion with metals, but also has an economical impact. Undesirable.

C) Production of composition To produce the composition of the present invention, the above-mentioned modified olefin polymer (which may contain a modified elastomer) and the hydroxyalkylphenylbenzotriazole compound may be uniformly mixed.

Alternatively, the modified olefin polymer, the unmodified olefin resin and/or elastomer, and the hydroxylalkylphenylbenzotriazole compound may be uniformly mixed.

Per K for producing the composition of the present invention, stabilizers against oxygen, light and heat, metal deterioration inhibitors, flame retardants, plasticizers commonly used in the field of olefin resins,
Additives such as lubricants, fillers, antistatic agents, and electrical property improvers may be added to the extent that they do not essentially impair the properties of the composition of the present invention.

Examples of the mixing method include the above-mentioned triblend method and melt mixing method, but the melt mixing method is preferable in order to obtain a uniform composition. Further, a more uniform composition can be obtained by triblending in advance and melt-kneading the resulting mixture.

Furthermore, during the extensive pre-blending that is commonly practiced in this field, the hydroxylalkylphenylbenzotriazole compound must be mixed with an inert, yet volatile organic solvent (e.g., acetone, toluene, xylene).
This solution is mixed with the polyolefin resin of the present invention to create a so-called master patch containing a high concentration of the hydroxylalkylphenylbenzotriazole compound, and then the olefin resin or modified olefin polymer is added to the master patch. , the elastomer may be mixed in the above composition ratio.

The conditions for melt crosstalk are the temperature at which commonly used hydroxylalkylphenylbenzotriazole compounds [for example, 130°C for 2-(2-hydroxyl-5-methyl-phenyl)-2H-benzotriazole
℃] and the adhesive resin composition obtained in this way has extremely excellent salt water resistance and good long-term adhesive durability, as is clear from the examples below.

(m) Laminate with metals As mentioned above, the adhesive resin composition has not only excellent salt water resistance but also good adhesive properties, so it can be laminated with various metals and used as various excellent industrial materials. be able to.

Examples of metals include iron, aluminum, copper, lead, zinc, tin, and nickel, and alloys containing these metals as main components. The shapes of these metals are
Powder, flake, filament (fiber), tubular, rod-shaped,
Examples include plate-like, foil-like, lump-like, and linear shapes.

The surfaces of these metal features may be left untreated or are typically subjected to surface treatments commonly used in this field of lamination (e.g. blasting, chemical conversion, cynic acid treatment,
Chromate treatment, plating treatment) may be used.

In addition, various types of primers (for example,
It may also be one that has been treated with a polyurethane-based primer, a urethane-based primer, a polyester-based primer, a polyethylene-based primer, or a titanate-based glitter.

In order to produce the laminate of the present invention, the above-mentioned composition may be used as it is by extrusion molding, injection molding, compression molding, blow molding, inflation, T-die methods, etc., which are generally practiced in this field. A molded product may be produced by a film forming method such as a round die method or a sheet forming method, and a laminate may be produced from the resulting composition by the method described below. In addition, the composition and other materials (e.g., ethylene polymer, propylene polymer)
They may also be thermocompression bonded while simultaneously being molded (for example, by coextrusion) (for example, in the production of electric wire coatings, steel pipe coatings, etc.). Furthermore, a desired laminate can be manufactured by thermocompression bonding the molded product manufactured as described above and other materials in the same manner.

When the composition of the present invention or a molded article obtained by shaping the composition is laminated with metal, the temperature is higher than the softening point of the composition of the present invention, preferably higher than the melting temperature, and the composition is It must be carried out at a temperature below which each of the constituent components decomposes and deteriorates.

In addition, thermocompression bonding methods include using a roll, press, etc. while heating with a hot roll, hot plate, infrared heater, heated steam, electromagnetic induction, etc. alone or in combination.
Alternatively, a method of applying reduced pressure and adhesion, such as known methods such as crosshead and round coating, may also be used.

It is not necessary to adopt a specific heating method and compression bonding method, and any commonly used method may be used.

In this way, it is possible to obtain a laminate with metal that has excellent salt water resistance and adhesive durability as described above. In particular, steel pipes and steel plates coated with various ethylene resins, ethylene-vinyl acetate copolymers, and propylene resins using the composition of the present invention as an adhesive layer can be used in pipelines for transporting gas, oil, etc. As a cable tube for electric wires, etc.
It is also useful as an underwater construction material or a material for quay walls.

[Examples and comparative examples]

Hereinafter, the present invention will be explained in more detail with reference to Examples.

The peel strength was expressed as the resistance value when a test piece having a width of 1O+m was peeled off at an angle of 90 degrees using a tensile tester at a rate of 50 sheets/min.

Regarding salt water resistance, the sample was immersed in 80°C 3-chloride saline solution for 8 hours, then taken out into the air and incubated at room temperature for 16 hours.
The condition of leaving for a period of time was set to 1 cycle, and after 7 cycles, the peel strength was measured in the same manner, and the retention rate (Q) with respect to the strength before immersion was determined.

The modified olefin polymers used in the Examples and Comparative Examples were manufactured as follows.

Linear ethylene-butene-1 copolymer with MFR (1) of 1.0jF-710 min [density 0.92177 cm3,
3100 parts by weight and 0.012 parts by weight of 2,5-dimethyl-2,5-di(hereinafter referred to as r P E (a) J).
Tertiary-butylperoxy)hexane was pre-triblended for 2 minutes using a Henschel mixer. Then, 0.40 parts by weight of anhydrous malein (hereinafter referred to as "legs") was added, and dry blending was carried out for 2 minutes using a Henschel mixer. The thus obtained mixture was melt-kneaded at a temperature of 260° C. using a non-pent extruder (L/D 30, diameter 4 Q yx*) to produce MAR-modified PE (a). Obtained “
When the leg-modified PE(a) J (hereinafter referred to as "modified product (■)") was measured by infrared absorption spectroscopy, the amount of MAR added was 0.38% by weight.

The PE (a) glue used in producing the modified product (1) had an MFR (1) of 0.8? /10 min linear ethylene-hexene-1 copolymer C density o, 9t7p/
10 minutes, hereinafter referred to as rpE(b)].
As in the case of the modified product (1) above, r MAH modified PE
(b) J [hereinafter referred to as [modified product QI]] was produced.

When the obtained modified product (n) was measured in the same manner as above,
The amount of MAR added was 0.38% by weight.

rPE(c)J] 100 parts by weight and 0.01 part by weight of 2,5-dimethyl-2,5-di(tertiary-butylperoxy)hexane were added in the same manner as in the case of modified product (I). I did a triblend. Then, 0.33 parts by weight of MAH
was added and tri-blend was performed in the same manner.

The mixture thus obtained was melt-kneaded at a temperature of 215°C in the same manner as in the case of modified product (I), and MAH-modified P.
E(c) (hereinafter referred to as "modified product (■)") was produced.

When the obtained modified product (I[I) was measured in the same manner as above, the amount of MAR added was 0.31% by weight.

100 parts by weight of an ethylene-propylene random copolymer (hereinafter referred to as rPPJ) having an MFR (2) of 0.6 P/10 minutes and an ethylene copolymerization ratio of 2.2% by weight;
1.5 parts by weight of benzoyl peroxide and 2.0 parts by weight
The parts by weight were triblended in the same manner as in the case of modified product (1). The resulting mixture was subjected to vented extrusion (L/
MAH modified PP (hereinafter referred to as "modified product (I
V) was produced. When the obtained modified product (IV) was measured in the same manner as above, the amount of MAR added was 0.70.
% by weight.

Examples 1 to 7, Comparative Examples 1 to 4 Modified products (1) whose respective blending amounts are shown in Table 1
, MFR is 2.2? A linear ethylene-butene-1 copolymer [density 0.9211-/C, hereinafter referred to as rP
E(d)J] and 2-(2-hydroxy-5-
methyl-phenyl)-2H-penztriazole [hereinafter referred to as "compound (1)"] and 0.0% as an antioxidant.
08 parts by weight of interaerythrityl-tetrakis (3-(
3,5-di-tertiary-butyl-4-hydroxyphenyl) f-ropionate] and 0.06 parts by weight of simiristyl-thio-dipropionate were blended in an extruder (diameter 50o1) equipped with a Dalmage screw.
The mixture was kneaded while melting at a temperature of 210° C. to produce each (composition).

Each pellet obtained was pressed to a thickness of 2 tm using a press.
A press sheet with a size of 150 m x 7 Qsaa was prepared. JISG whose surface has been degreased with toluene in advance
The thickness is 3.2 inches and the size is 15 mm by grid-plasting rolled steel material of 8841 specified in 3101.
The rolled steel sheet of Qsn
Each laminate was manufactured by immersing it in cold water whose temperature was controlled to 5° C. for 2 minutes. The peel strength and salt water resistance of each of the obtained laminates were measured. The results are shown in Table 1.

(The following is a blank space) Examples 8 to 10, Comparative Examples 5 and 6 Modified substances ω) whose respective blending amounts are shown in Table 2
PE (d), MF'R (1) is 4.0. P/10 minutes, the copolymerization ratio of butene-1 is 10 mol, and the crystallinity of 10-1 as measured by
, BJ) and azole (A) and 0.08 parts by weight of pentaerythrityl-tetrakis (3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) as an antioxidant and Pellets (composition) were prepared in the same manner as in Example 1, with the addition of 0.06 parts by weight of dimyristylthiodigropionate.

A press sheet was produced from each of the obtained pellets in the same manner as in Example 1. Each laminate was manufactured in the same manner as in Example 1 using each press sheet and the rolled steel plate used in Example 1. The peel strength and salt water resistance of each of the obtained laminates were measured. The results are shown in Table 2.

Example 11.12. Comparative Examples 7 and 8 Modified product (m) s o parts by weight, density 0.92077c
m”) and has an MFR (1) of 2.1jL/10 min [hereinafter referred to as rPE(e)J] 50
Weight part, o, 4ffi! part of 2-(2-hydroxy-5
-g3i-butyl-phenyl)-ZU-penztriazole, 0.05 parts by weight of 0.04 parts by weight of simiristyl-thio-dipropionate was mixed in the same manner as in Example 1 (Example 11).

50 parts by weight of modified product (III), 35 parts by weight of PE (e
), 15 parts by weight of E, B, 0.40 parts by weight of 2-(
2-Hydroxy-5-tertiary-butyl-phenyl)-2
H-penztriazole, O,OS parts by weight of intererythyl-tetrakis(3-(3,5-di-tert-butyl-4-hydroxy-7-2-l)propionate and 0
．． 0.4 parts by weight of similystyl-thio-dipropionate was mixed in the same manner as in Example 1 (Example 12).

In Example 11, when producing the composition, the composition was as follows:
-(2-hydroxy-5-tertiary-butyl-phenyl)
-2H-penzotriazole was not included.
A composition was produced in the same manner as in Example 11 (Comparative Example 7).

In addition, 2-(2-hydroxy-5-tertiary-butyl-phenyl)-2H-pen:,') which was blended when producing the composition in Example 12! A composition was produced in the same manner as in Example 12, except that 77sol was not blended (Comparative Example 8).

Press sheets were prepared from the compositions obtained in Examples 11 and 12 and Comparative Examples 7 and 8 in the same manner as in Example 1. Each of the obtained press seeds and the rolled steel plate used in Example 1 were heat-pressed in the same manner as in Example 1, and
Each laminate was manufactured.

When we measured the salt water resistance of each laminate, the retention rate was as follows:
In Examples 11 and 12, they were 35.4% and 37.9%, respectively, while in Comparative Examples 7 and 8, they were 9.4 inches and 8.7 inches, respectively.

Example 13, Comparative Example 9 Modified product (IV) 20 parts by weight, 70 parts by weight of pp, ethylene with a crystallinity of 0 as determined by X-ray diffraction and a copolymerization ratio of progylene of 26% by weight - 10 parts by weight of propylene random copolymer distomer, 0.60 parts by weight of compound (A), and the same amount of antioxidant as in Example 1 are kneaded while melting in the same manner as in Example 1 to produce a composition. (Example 13).

A composition was produced in the same manner as in Example 13, except that the azole (4) blended in Example 13 was not blended (
Comparative Example 9).

Press sheets were prepared from each of the compositions thus obtained in the same manner as in Example 1. Each of the obtained presses and the rolled steel plate used in Example 1 were heated to 190° C. in the same manner as in Example 1 to create each laminate.

The salt water resistance of each of the obtained laminates was measured.

The retention rate was 43% in Example 13, while it was 11.1% in Comparative Example 9.

〔Effect of the invention〕

As described above, the composition of the present invention and the laminate of the composition and metal, including the manufacturing method thereof, exhibit the following effects.

(1) The hydroxylalkylphenylbenzotriazole compound to be blended into the composition of the present invention is easily available, and can be easily blended in the same way as ordinary additives. -(2) Further, in improving salt water resistance, a relatively small amount of the compound exhibits a remarkable effect.

(3) As mentioned above, laminates with metals exhibit excellent adhesion and retention even when in contact with salt water or corrosive solutions, so even if used for a long time,
Demonstrates extremely excellent performance.

The laminate of the adhesive resin composition and metal of the present invention can be used in many directions in order to exhibit the above effects. Typical uses are shown below.

(1) Coated steel pipes (for those used in seawater, buried soil, or similar atmospheres) (2) Electric wire coating (3) Coated steel plate

Claims (2)

[Claims] (1) At least 0.1% by weight of an olefinic polymer modified with an unsaturated carboxylic acid and/or its anhydride
An adhesive resin composition comprising 0.1 to 1.0 parts by weight of a hydroxylalkylphenylbenzotriazole compound represented by the following formula (I) per 100 parts by weight of a polyolefin resin. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R is an alkyl group with 1 to 8 carbon atoms.) (2) Hydroxylalkylphenyl represented by the following formula (I) per 100 parts by weight of an olefin polymer containing at least 0.5% by weight of a polyolefin resin modified with an unsaturated carboxylic acid and/or its anhydride. A laminate formed by laminating an adhesive resin composition containing 0.1 to 1.0 parts by weight of a benzotriazole compound as an adhesive layer to a primer layer of metal or a primer-treated metal. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R is an alkyl group with 1 to 8 carbon atoms.)