JPH0142825B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a metal composite material using a polyamide adhesive composition. Metal composite materials are known which consist of plates of metal material adhered to both surfaces of an adhesive layer. Attempts have been made to use polyamide resin as the adhesive layer of such metal composite materials, and research is being conducted to improve this. In other words, when a polyamide homopolymer is used alone as a polyamide resin, it cannot be said to have sufficient adhesive strength, so in order to increase the adhesive strength, various reactive monomers are added during the production of the polyamide resin. Adhesion that utilizes modification of polyamide resin such as making it into a binary copolymer or ternary copolymer, combination of epoxy primer, or modification of polyamide resin by adding a third component to form a composition. Improvements in properties have been proposed for some time. Among these, polyamide resins that are made into copolymers or ternary copolymers tend to lose the excellent heat resistance that is a characteristic of polyamide resins.
The melting point of the resulting resin also decreases, so if the bonded material, such as a steel plate, is subjected to a high-temperature process such as baking in a later process, peeling may occur at the bonded portion. On the other hand, the method of applying a primer to the surface of the material to be bonded and then bonding with an adhesive results in lower workability, longer bonding time, lower high-temperature peel strength, lower flexibility, and higher cost. This is not a practically desirable method as it often causes problems. In addition, as an example of improving hot melt type polyamide resin adhesives, an adhesive composition in which polyethylene is blended with polyamide resin (Japanese Patent Laid-Open No. 51-59936
(Japanese Unexamined Patent Application Publication No. 1983-62833), an adhesive composition for can making containing an ionomer blended with a polyamide resin,
Examples include an adhesive composition (Japanese Unexamined Patent Publication No. 48-92439) in which a specific organosilicon compound is blended with a polyamide resin. Although the performance of polyamide resin as a hot melt adhesive is improved to some extent by the addition of these additive components, in reality, in most cases the surface of the material to be bonded is pre-primed, and therefore, These adhesive compositions are also not sufficient to achieve strong adhesion without primer treatment. The present invention provides a hot melt type polyamide adhesive composition that further improves the properties of those conventionally known polyamide adhesives, and in particular does not require primer treatment on the surface of the metal material plate that is the adherend material. The present invention provides a metal composite material using a hot melt type polyamide adhesive composition as an adhesive layer. That is, the metal composite material of the present invention contains 100 parts by weight of polyamide resin, 2 to 50 parts by weight of ethylene/propylene rubber and/or ionomer, and an aminosilane compound based on the weight of the total resin component.
This is a metal composite material consisting of an adhesive layer made of a polyamide adhesive composition containing 0.1 to 5% by weight, and metal material plates adhered to both surfaces of the adhesive layer. Next, the present invention will be explained in detail. The polyamide resin used as a base material in the adhesive composition for a metal composite material of the present invention is not particularly limited, and may be one that has been conventionally used as a base material for polyamide adhesives or polyamide adhesive compositions. Alternatively, various polyamide resins proposed for use in these applications can be used. Examples of such polyamide resins include nylon 6, nylon 11, nylon 12,
Examples include various nylon homopolymers such as nylon 66 and nylon 610, and copolymerized nylons thereof. These polyamide resins may be used alone or in combination. Furthermore, a polyamide copolymer may be mixed with these polyamide homopolymers for use as long as it does not contradict the purpose of the adhesive composition for the metal composite material of the present invention. As the ethylene/propylene rubber, various conventionally known ethylene/propylene rubbers (EPR) can be used, but particularly preferred ethylene/propylene rubber has a propylene content of about 20 to 30% by weight. be. Furthermore, in the present invention, the ethylene/propylene rubber may contain other copolymer components, such as ethylene/propylene/diene rubber. Ionomers are thermoplastic resins in which long-chain molecules are linked by ionic bonds, and the carboxyl groups of each molecule are usually cross-linked by monovalent or polyvalent metal cations. . Typical ionomers are copolymers of unsaturated hydrocarbons such as ethylene, propylene, and butylene and unsaturated carboxylic acids such as maleic acid, acrylic acid, and methacrylic acid.
Monovalent metal cations such as potassium, or calcium, magnesium, barium, zinc, iron,
Examples include thermoplastic resins crosslinked with polyvalent metal cations such as copper and silver. Specifically, Surlyn (trademark of DuPont, USA, a copolymer of ethylene and methacrylic acid crosslinked with sodium ions or zinc ions) and Copolene (trademark of Asahi Dow Corporation, a copolymer of ethylene and acrylic acid) Examples include products such as polymers crosslinked with metal ions). In the present invention, the above ethylene/propylene rubber and/or ionomer is made of polyamide resin.
2 to 50 parts by weight per 100 parts by weight (preferably,
(5 to 30 parts by weight), and if the amount exceeds the upper limit of this range or is less than the lower limit of this range, it will be difficult to achieve the object of the present invention. In the present invention, it is particularly preferable to use ethylene/propylene rubber and an ionomer together. In this case, 1 to 100 parts by weight of ethylene/propylene rubber should be added to 100 parts by weight of polyamide resin.
15 parts by weight, and preferably 1 to 35 parts by weight of the ionomer. Aminosilane compounds can be used for glass, inorganic fillers,
It is already known for use as a surface modifier for synthetic resins and the like. The aminosilane compound used in the present invention can be selected from among these various aminosilane compounds. Examples of such aminosilane compounds include α-aminoethyltriethoxysilane, γ-aminopropyltriethoxysilane, α-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, α-aminobutyltriethoxysilane, N-
Examples include β-(aminoethyl)-γ-aminopropyltrimethoxysilane. The above aminosilane compound is added at 0.1% by weight based on the weight of all resin components (polyamide resin and ethylene/propylene rubber and/or ionomer)
It is necessary to blend at a ratio of ~5% by weight,
If the amount exceeds the upper limit of this range and if the amount is less than the lower limit of this range, it will be difficult to achieve the objectives of the present invention. In addition, in the adhesive composition for the metal composite material of the present invention, the preferred blending amount of the aminosilane compound is the total resin component (polyamide resin,
and ethylene propylene rubber and/or ionomer). The adhesive composition for the metal composite material of the present invention includes, for example, each component, namely, polyamide resin,
A predetermined amount of ethylene/propylene rubber and/or ionomer, and an aminosilane compound are dry blended, and this is heated using an extruder and molded into various forms such as film, sheet, filament, and granule. . As the heating conditions, a temperature is selected that is higher than the melting temperature of the polyamide resin and lower than the decomposition temperature of the aminosilane compound. The metal material plate of the metal composite material of the present invention includes:
In particular, metal material plates such as steel plates, surface-treated steel plates, aluminum plates, and copper plates can be suitably used. In particular, when a surface-treated steel plate such as a chrome-plated steel plate is used, a metal composite material bonded with high adhesive strength can be obtained. The metal material plates in the present invention do not require any special adhesion imparting operation (for example, primer treatment on the surface of the material to be adhered) other than the degreasing operation normally performed when adhering them. However, if desired,
This does not preclude the use of these special adhesion imparting operations in combination. When manufacturing the metal composite material of the present invention, the operation of adhering metal material plates to both surfaces of the adhesive layer made of the polyamide adhesive composition is the same as the adhesion operation using a conventional hot melt type polyamide adhesive. Just follow the instructions. For example, a typical batch method involves placing a film-like adhesive on a stationary metal plate, placing a metal plate of the same or different type on top of it, and applying pressure while heating. Alternatively, when feeding two coiled steel plates into the pressure section of a steel belt laminator, insert a film or viscous liquid adhesive between the two steel plates and apply this under heat. Various methods can be used, including a continuous method, typified by a pressure method. Next, examples of the present invention will be shown. Example 1 100 parts by weight of polyamide (nylon 6), 17 parts by weight of ionomer (Copolene, trademark of Asahi Dow Co., Ltd., a carboxylic acid copolymer of ethylene and acrylic acid cross-linked with magnesium ions), ethylene-propylene rubber (Propylene content: 25% by weight) 4.2 parts by weight, and aminosilane (N-β
-(aminoethyl)-γ-aminopropyltrimethoxysilane) was dry blended and extruded using an extruder while heating at 250 to 260°C to form a sheet (thickness: 0.7 mm). ). The sheet-like adhesive described above is sandwiched between two chrome-plated steel plates (thickness: 0.2 mm) that have been degreased with an alkaline degreaser for steel (Metazol 400, trademark of Marubishi Yuka Co., Ltd.), and this is then bonded to a hot plate. Place it on top of 245
Pressure bonding was carried out at a temperature of 8 kg/cm ² for 8 minutes at a temperature of 8 kg/cm 2 , and then allowed to cool naturally. The adhesive strength of the composite steel plate obtained as described above was measured by a T-peel test method according to JIS K-6853. The measurement results are shown in Table 1 (described later). Comparative example 1 Polyamide (nylon 6) as adhesive component
A sheet adhesive was prepared in the same manner as in Example 1 except that only 100 parts by weight and 30 parts by weight of the ionomer (corpolene) were used, and then a composite steel plate was manufactured.
Adhesive strength was measured using a similar method. The measurement results are shown in Table 1 (described later). Comparative Example 2 Polyamide (nylon 6) as adhesive component
A sheet adhesive was prepared in the same manner as in Example 1, except that only 100 parts by weight and 10 parts by weight of ethylene/propylene rubber (propylene content: 25% by weight) were used, and then a composite steel plate was manufactured and the same procedure was carried out. Adhesive strength was measured using a method. The measurement results are shown in Table 1 (described later). Reference Example 1 Two chrome-plated steel plates (same as the degreased plate used in Example 1) whose surfaces have been subjected to primer treatment (using an epoxy resin primer) are used as materials to be adhered. The sheet adhesive prepared in Comparative Example 1 was placed between them, and Example 1
A composite steel plate was manufactured in the same manner. The adhesive strength of this composite steel plate was measured using the same method.
The measurement results are shown in Table 1 (described later). Reference Example 2 Two chrome-plated steel plates (same as the degreased steel plate used in Example 1) whose surfaces were subjected to primer treatment (same treatment as Reference Example 1) were used as materials to be adhered. The sheet adhesive prepared in Comparative Example 2 was placed between the two, and a composite steel plate was produced in the same manner as in Example 1. The adhesive strength of this composite steel plate was measured by the same method. The measurement results are shown in Table 1.

[Table] Comparative Example 2 Easily peeled off by hand -

Claims (1)

[Claims] 1 100 parts by weight of polyamide resin, 2 to 50 parts of ethylene/propylene rubber and/or ionomer
an adhesive layer made of a polyamide adhesive composition containing 0.1 to 5% by weight of an aminosilane compound based on the total weight of the resin components; and a metal material attached in an adhesive state to both surfaces of the adhesive layer. A metal composite material consisting of a plate.