JPS619474A - Bondable resin composition and laminate thereof - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having good corrosion resistance and adhesion to metal, by reacting a base reaction product between an ethylene polymer resin and a rubber with an unsaturated compd. contg. an amide group. CONSTITUTION:100pts.wt. ethylene polymer resin (e.g. PE having a density of 0.93g/ml or below) is reacted with 10-300pts.wt. rubber (e.g. ethylene/propylene rubber) to obtain a base reaction product. 100pts.wt. said base product is reacted with at least 0.5pt.wt. unsaturated compd. contg. an amide group (e.g. acrylamide) in the presence of a radical polymn. initiator (e.g. methyl ethyle ketone peroxide) in a good solvent (e.g. hexane) for said base product at 100-300 deg.C to obtain a bondable resin compsn. A sheet material such as a thermoplastic resin or rubber sheet is bonded to a metallic substrate through said compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Industrial application field The present invention relates to an adhesive resin composition and a laminate thereof, which exhibit particularly good adhesion to metals and corrosion resistance. The present invention relates to an adhesive resin composition and a laminate thereof, in which 10 to 300 parts by weight of a thermoplastic resin composition is reacted with an unsaturated compound having an amide group.

(b) Conventional technology Ethylene polymers such as polyethylene are widely used as surface coating materials and adhesives for metals, plastics, paper, glass, etc., due to their excellent water resistance, chemical resistance, flexibility, etc. has been done. Ethylene-based polymers are basically non-polar polymers made of carbon and hydrogen and have poor adhesive properties, so in many cases, polymers with polar groups introduced to give them adhesive properties are used. . This includes a method of mixing an ethylene polymer with a polymer or monomer having a polar group, a method of copolymerizing it with a polar compound during ethylene polymerization,
It is manufactured by reacting a polar compound with an ethylene polymer by grafting or adding it, but many methods involve reacting a polar compound because it has little negative effect on the ethylene polymer itself and provides good adhesive strength. It is used.

However, even with these adhesive resins, it is not possible to obtain a product that satisfies all uses. For example, for metals such as iron, resins made by reacting polyethylene with unsaturated carboxylic acids and their derivatives are suitably used, but the durability of the adhesive, such as water resistance and salt water resistance, is insufficient, and it is difficult to use with reed seawater. It is not preferable as a coating material for steel pipes that pass through pipes, etc., or for steel pipes that are buried underground. Therefore, for this type of application, a method has been adopted in which steel pipes have been pretreated with primers such as epoxy resins or organic silicon compounds, which have excellent corrosion resistance, and are coated with the adhesive polyethylene described above, but the process is complicated and is not economical. Therefore, there has been a desire for an adhesive resin with excellent corrosion resistance without the need for primer treatment.

(c) Problems to be solved by the invention In view of the above-mentioned current situation, the inventors conducted intensive research to develop an adhesive resin that does not require primer treatment and has high adhesive strength and excellent corrosion resistance, and as a result, the present invention has been developed. It has reached. The present invention will be explained in more detail below.

(A) 100 parts by weight of an ethylene polymer and (
B) an adhesive resin composition in which at least 0.5 parts by weight of (C) an unsaturated compound having an amide group is reacted with 100 parts by weight of a reaction substrate consisting of 10 to 300 parts by weight of rubber, and the adhesive resin composition; At least two adhesives directly adhered to a substrate using a resin composition containing the adhesive resin composition.
It provides a laminate consisting of layers, and has particularly remarkable effects on initial adhesive strength with metals and corrosion resistance.

(A) Ethylene-based polymer resin used in the present invention is linear polyethylene obtained by polymerizing ethylene with a Ziegler-based catalyst or chromium-based catalyst, if necessary, in the presence of an α-olefin, and polymerized using a radical initiator. Examples include polyethylene having long chain branches, copolymers of ethylene and monomers having polar groups such as vinyl acetate, acrylic acid, and derivatives thereof. This is polyethylene with a density of 0.93 g/ml or less. Examples of α-olefins include propylene, butene-1, hexene-1,4-methylpentene-1, and octene-1. If the density is 0.93 f//m1 or more, the composition tends to have poor adhesive strength and corrosion resistance.

Another preferred ethylene polymer resin (A) is a copolymer of ethylene and a monomer having a polar group. Monomers with polar groups include vinyl acetate, allyl acetate, acrylic acid, methyl acrylate, ethyl acrylate,
Butyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, maleic acid, maleic anhydride, diethyl maleate, diethyl fumarate, acrylonitrile, vinyl chloride, styrene,
Examples include acrylamide, vinylpyrrolidone, methylvinylketone, trimethoxyvinylsilane, and triethoxyvinylsilane. Among these, vinyl acetate and ethyl acrylate are particularly preferred because they are inexpensive, easy to handle, and provide compositions with excellent adhesive strength and corrosion resistance.

Antioxidants, ultraviolet absorbers, stabilizers, lubricants, plasticizers, dyes, pigments, fillers, etc. can be added to these ethylene copolymer resins as necessary.

Rubber (B) used in the present invention includes ethylene-propylene rubber, ethylene-propylene-diene copolymer, ethylene-butene-1 random copolymer polyisobutylene, styrene-butanoene block copolymer, thermoplastic polyester Rubber, thermoplastic polyurethane rubber, liquid polybutadiene, polybutadiene rubber, chloroprene rubber, styrene-butadiene rubber, phtadiene-acrylonitrile-styrene rubber, natural rubber rubber, or mixtures thereof. Among these, polyolefin rubbers such as ethylene-propylene rubber, ethylene-butene-1 random copolymer, polyinobutylene, and styrene-butadiene block copolymers have excellent compatibility with ethylene copolymer resins. Particularly preferred.

The amount of rubber (B) used is 1 ethylene polymer resin.
It needs to be 10 to 300 parts by weight per 00 parts by weight. If it is less than 10 parts by weight, the composition will have poor adhesiveness and corrosion resistance, and if it exceeds 300 parts by weight, the tensile strength etc. of the composition itself will decrease, making it undesirable as an adhesive resin.

Examples of the unsaturated compound having an amide group (0) used in the present invention (hereinafter referred to as an amide compound) include acrylamide, methacrylamide, N-methylacrylamide, N,N-dimethylacrylamide, N-acetylacrylamide, and maleamide. , maleic acid monoamide, N
, N'-diallylformamide and the like. Among these, acrylamide, methacrylamide, maleamide, etc., and especially acrylamide, are particularly preferred because of their high reactivity to ethylene polymer resins. The reaction amount of this amide compound is at least 0.5 parts by weight based on 100 parts by weight of (A) ethylene polymer resin and (B) rubber (hereinafter referred to as "reaction substrate"). If the reaction amount is less than this, the adhesive strength
Corrosion resistance is poor, causing problems in practical use.

In the present invention, various methods can be used to react the amide compound with the reaction substrate. Basically, this is carried out by creating active sites on a reactive substrate and adding an amide compound to these active sites. Therefore, it is presumed that the product is a composition in which a monomer or polymer of the amide compound is grafted onto the reaction substrate, and a portion of the product contains a homopolymer of the amide compound. There are several methods of creating active sites in the reaction substrate, such as using radical initiators, irradiating ionizing radiation or light, using plasma, and generating thermal radicals at high temperatures, but the equipment is inexpensive and A method using a radical initiator is suitable because it is simple and has high reactivity. Examples of radical initiators include organic peroxides, azonium, etc., and examples of organic peroxides include ketone peroxides such as methyl ethyl ketone peroxide and chlorhexaton peroxide, 1,1
-bis(t-butylperoxy) 3,3. δ-trimethyl/chlorohexane, 1. Peroxyketals such as l-bis(1-butylperoxy7)/chlorohexane, 1--
- Hydroperoxides such as butyl hydroperoxide, cumene hydroperoxide, diinopropylbenzene hydroperoxide, di-t-butyl peroxide, t-butyl dicumyl peroxide, dicumyl peroxide, α, α'-bis(1-butylperoxyinoprobyl)benzene, 2,5-dimethyl-2,5-cy(t-butylperoxy)hexane, 2
, 5-dimethyl-2,5di(t-butylperoxy)hexyne-3 and other dialkyl peroxides, benzoyl peroxide, octanoyl peroxide, decanoyl peroxide and other dialkyl peroxides, di-
Peroxydicarbonates such as isopropyl peroxydicarbonate and di-n-propylperoxydicarbonate, peroxyesters such as t-butylperoxyacetate, t-butylperoxyisobutyrate, and t-butylperoxybenzoate, etc. There is. Azonitriles include azobisinobutyronitrile, azobisinoprobionitrile, and the like. These are appropriately selected depending on reaction conditions such as reaction solvent and reaction temperature.

There are various methods for reacting an amide compound with a reaction substrate using a radical initiator. There are two methods: a method in which the reaction is carried out in a solution state using a medium that is a good solvent for the reaction substrate (solution reaction), a method in which the reaction is carried out in a suspended state using a medium that is a poor solvent for the reaction substrate (suspension reaction), and a reaction medium. Examples include a method in which the reaction substrate is heated to a temperature above its melting point or softening point and reacted while kneading (melt reaction) without using the reaction substrate. Media used in solution reactions include aliphatic hydrocarbons such as hexane, heptane, octane, cyclohexane, and decalin, aromatic hydrocarbons such as benzene, toluene, xylene, and tetralin, dichlorobenzene, chloroform, carbon disulfide, and tetralin. Examples include polar solvents such as carbon chloride and trichloroethane. A suitable medium for suspension reactions is water and the like. For the melt reaction, extruders, kneaders, Banbury mixers, rolls, etc., which are generally used in the processing of plastics and rubber, are used. Among these methods, solution reaction is generally preferred since it can increase the amount of amide compound reacted. The reaction conditions in this case are appropriately selected. The temperature must be higher than the temperature at which the reaction substrate melts in the medium and at which the radical initiator is sufficiently decomposed and generates radicals within the reaction time. On the other hand, if the temperature is too high, the reaction substrate or amide compound may decompose or cause side reactions, so a temperature in the range of approximately 100 to 300°C is preferable.

(e) Function The adhesive resin composition obtained in this way has excellent adhesive strength and is widely used for coating other materials by dissolving it in a solvent and applying it, powder coating, etc., or as a laminated material, etc. be able to.

Further, the adhesive resin composition may be made of polyethylene, polypropylene, ethylene-α-olefin copolymer, ethylene-
It is also possible to add and dilute a thermoplastic resin described below such as an olefin polymer such as a vinyl acetate copolymer.

Another invention of the present invention is to produce a laminate consisting of at least two layers directly adhered to a base material using the above-mentioned adhesive resin composition or an adhesive resin composition containing the adhesive resin composition as a component. This is what we provide.

As the base material, a sheet material made of thermoplastic resin, rubber, etc., a metal foil, a metal layer, a wire mesh, and other materials can be used.

Thermoplastic resins used for the above base material include low, medium, and high density polyethylene, polypropylene, polybutene-1,
Homopolymers such as poly-4-methylpentene-1, copolymers with other α-olefins mainly composed of ethylene or propylene, ethylene-vinyl acetate copolymers or saponified products thereof, ethylene-unsaturated Polyolefin resins containing copolymers with other polar monomers based on α-olefins such as ethylene or propylene, such as copolymers with carboxylic acids and their derivatives;
Polystyrene resin, polyacrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, nylon-6
, nylon-6,6, nylon 7-11. Nylon-12
．． Polyamide resins such as aromatic polyamides, polycarbonate resins, cellulose resins, polyethylene terephthalate
Notes, polyester resins such as polybutylene terephthalate, fluorine resins such as polytetrafluoroethylene, polyimide resins, polyamideimide resins, polyether/etherketone resins, polyether sulfone resins, polysulfone resins, polyphenylene oxide resins, polyphenylene sulfide resins and polyacetal resin.

Examples of the base rubber include polybutadiene, polyisoprene, neoprene rubber, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, styrene-
Synthetic rubbers such as butadiene copolymer, styrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer, butyl rubber, polyurethane rubber, chlorosulfonated polyethylene, chlorinated polyethylene, fluororubber, thiokol, and natural rubber are listed. I get kicked.

Examples of the base metal include metal foils, metal plates, wire meshes, and punching plates made of metals such as iron, aluminum, copper, zinc, brass, nickel, tin, stainless steel, tinplate, and galvanized iron.

Further, as the base material of the present invention, a sheet in which the above-mentioned thermoplastic resin is blended with a filler can also be used.

These filling phases include calcium carbonate, magneum carbonate, calcium sulfate, calcium sulfite, calcium silicate, clay, diatomaceous earth, talc, alumina, silica sand,
Glass powder, iron oxide, metal powder, antimony trioxide, graphite, silicon carbide, silicon nitride, silica, boron nitride, aluminum nitride, wood powder, carbon blank, mica, glass plate, sericite, pyrophyllite, aluminum flakes, Examples include graphite, Noras balloon, metal balloon, glass balloon, pumice, glass fiber, carbon fiber, graphite, whiskers, metal fiber, asbestos, organic fiber, and glass fiber.

The amount of the filler described in item 1 varies depending on the purpose of use, application, etc., but is usually blended in the range of 5 to 1000 parts by weight per 100 parts by weight of the thermoplastic resin.

1. The above-mentioned foamed or crosslinked thermoplastic resins can also be used.

The laminate with the above-mentioned various base materials does not have to have at least a two-layer structure, but it can also have a multi-layer structure of three or more layers (for example, metal/adhesive resin/polyolefin) depending on the use and purpose. It is preferable to use a laminated structure with a metal, particularly a laminate with iron, in which the adhesive resin of the invention exhibits its effectiveness most markedly.

Further, when the adhesive resin composition of the present invention is used in combination with the above-mentioned thermoplastic resin, it may be diluted so that the resin contains at least 0.5% by weight of functional groups containing amide groups.

The method for manufacturing the laminate of the present invention is not particularly limited,
For example, coating by extrusion molding, coextrusion, powder coating by fluid dipping, electrostatic coating, powder spraying, etc., or dissolving in a solvent and applying with a brush, etc.
Usual methods such as a method of heat-sealing an adhesive resin sheet can be used.

(f) Examples The present invention will be explained in more detail with reference to the following examples. In addition,
The test method is as follows.

Test method (1) Quantification of reaction amount of amide compound The reaction product is hot pressed to create a thin sheet and quantified by infrared spectroscopy.

(g) Adhesive strength Steel plate cleaned with xylene and butylcelonorb (5p
cc-3D) or adhere the reaction product to a nylon sheet by heat pressing (230°C).
A width-wide cut was made and the 180° peel resistance was measured using a tensile tester. 251III Displayed as adhesive strength per width.

(iii) Salt water resistance A laminate was prepared using the same method as above, a cross notch with a length of 80 mm was inserted, and the product was immersed in 3% saline solution kept at 40°C to measure the degree of salt water penetration. The measure of salt water resistance is expressed as the time it takes for an average of 2 cm of peeling to occur from the notch.

<Resin used> 1) Ethylene polymer resin (A) Linear low-density polyethylene made by copolymerizing ethylene and butene-1 L/7, MI-18g/10min, density -〇9
21g/cd (B) Same as above, Ml-15g710min, density-0.9
27,9/an(C) Copolymer of ethylene and ethyl methacrylate, MI-3, 39710 min, ethyl methacrylate content -14% by weight 2) Rubber (7) Styrene-butadiene broth copolymer shell Manufactured by Kagakusha [Califlex TR1102-KX65J (
(trade name) (a) Ethylene propylene rubber manufactured by Japan Synthetic Rubber Co., Ltd. J JSR-EPOIP j (trade name) ←) Polyisobutylene manufactured by Efnon Chemical Co., Ltd.
Trademark name) Example 1 1500 parts by weight of xylene, 100 parts by weight of ethylene polymer resin (A), 50 parts by weight of rubber (7), 10 parts by weight of acrylamide and 1 part by weight of dicumyl peroxide were charged into a glass reactor. After the system was sufficiently purged with nitrogen gas, the mixture was heated to 135° C. without stirring, and the reaction was carried out for 5 hours. The reaction mixture was poured into a large amount of cold acetone to precipitate the product. This was filtered and dried to obtain the composition of the present invention. The amount of acrylamide contained in this composition is 43% by weight, and the adhesive strength to steel plate is 18kg/25m
Adhesive strength to m-width, 6-nylon notebook is 30K.
g/2511 width, salt water resistance after breaking was more than 100 hours.

Comparative Example 1 The reaction was carried out in the same manner as in Example 1 except that no rubber was used. The amount of acrylamide contained in this reaction composition is 2.7% by weight, and the adhesive strength to steel plate is 8kli.
/25 mm width, and salt water resistance was 5 hours.

Comparative Example 2 The reaction was carried out in the same manner as in Example 1, except that the amount of rubber used in Example 1 was changed to 5 parts by weight. The amount of acrylamide contained in this reaction composition was 29% by weight, and the adhesive strength to the steel plate was 8.
kg/25m5+ width, salt water resistance was 6 hours.

Example 2 100 parts by weight of ethylene polymer resin (A), rubber (7)
A reaction composition was obtained in the same manner as in Example 1 except that 25 parts by weight was used. The amount of acrylamide contained in this composition is 4% by weight, and the adhesive strength to steel plate is 16k
g/25 width, salt water resistance was 50 hours.

Example 3 A reaction composition was obtained in the same manner as in Example 1, except that 100 parts by weight of (B) was used as the ethylene polymer resin. The amount of acrylamide contained in this composition is 41% by weight, and the adhesive strength to steel plate is 15 klJ / 25
The durability and salt water resistance were 100 hours or more.

Example 4 A reaction composition was obtained in the same manner as in Example 1, except that 100 parts by weight of (c) was used as the ethylene polymer resin. The amount of acrylamide contained in this composition is 44% by weight, and the adhesive strength to steel plate is] 9 kg/25
The salt water resistance was 100 hours or more in mm.

Comparative Example 3 The reaction was carried out in the same manner as in Example 4 except that no rubber was used. The amount of acrylamide contained in this reaction composition is 39% by weight, and the adhesive strength to the steel plate is 14kli.
/25 width, salt water resistance was 6 hours.

Example 5 A reaction was carried out in the same manner as in Example 1 except that 50 parts by weight of rubber and (a) 1 to 1 were used. The amount of acrylamide contained in this reaction composition was 42% by weight, the adhesive strength to a steel plate was 1.6 kg/25y width, and the surface 1 salt water resistance was 100 hours or more.

Example 6 Example 1 except that 50 parts by weight of rubber was used.
The reaction was carried out in the same manner. The amount of acrylamide contained in this reaction composition was 42% by weight, the adhesive strength to a steel plate was 15 klJ/25 mm, and the salt water resistance was 100 hours or more.

Example 7 A reaction was carried out in the same manner as in Example 1 except that 10 parts by weight of methacrylamide was used as the unsaturated compound having an amide group. The amount of methacrylamide contained in this reaction composition was 21% by weight, and the adhesive strength to the steel plate was 1.
3 kg/25 + url], and the salt water resistance was 50 hours.

Example 8 The reaction was carried out in the same manner as in Example 1, except that the amount of rubber used in Example 1 was changed to 150 parts by weight. The amount of acrylamide contained in the obtained reaction composition was 45 parts by weight, the adhesive strength to the steel plate was 9/25*i+width, and the salt water resistance was 100 hours or more.

(G) Effects of the Invention As mentioned above, the adhesive resin composition of the present invention not only adheres to various base materials, but also has particularly good adhesion to metals, and has excellent initial adhesive strength and durability of adhesive strength. For example, it has excellent peeling resistance when submerged in water or seawater.

The laminate with metal made using the adhesive resin composition of the present invention has excellent water resistance and salt water resistance without the need for conventional primer treatment. It can be used in harsh environments such as, and the laminate with metal plates can also be used as door panels for vehicles and the like.

Patent applicant Nippon Petrochemical Company, Ltd.
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Claims (7)

[Claims] (1) Reaction substrate 100 consisting of (A) 100 parts by weight of ethylene polymer resin and (B) 10 to 300 parts by weight of rubber
An adhesive resin composition in which at least 0.5 parts by weight of (C) an unsaturated compound having an amide group is reacted with respect to parts by weight. (2) The ethylene polymer resin is a linear copolymer of ethylene and α-olefin, and its density is 0.93 g.
/ml or less
The adhesive resin composition described in . (3) The adhesive resin composition according to claim 1, wherein the ethylene polymer resin is a copolymer of ethylene and a polar group-containing monomer. (4) The adhesive resin composition according to any one of claims 1 to 3, wherein the unsaturated compound having an amide group is acrylamide. (5) Reaction substrate 100 consisting of (A) 100 parts by weight of ethylene polymer resin and (B) 10 to 300 parts by weight of rubber
An adhesive resin composition reacted with at least 0.5 part by weight of (C) an unsaturated compound having an amide group or a composition containing the adhesive resin composition as a component is directly applied to a substrate. A laminate consisting of at least two layers bonded together. (6) The laminate according to claim 5, wherein the unsaturated compound having an amide group is acrylamide. (7) The laminate according to claim 5 or 6, wherein the base material is metal.