JPH0223587B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a laminate with metal using an adhesive polyolefin composition having good adhesion to various substrates. [Prior Art] Although polyolefin resins are used in various fields, they have a drawback in that they cannot be used for adhesive purposes because of their poor adhesive properties. Therefore, various improvement methods have been proposed to impart adhesiveness to polyolefin resins. For example, a method has been proposed in which a graft reaction between polyolefin and an unsaturated compound having a polar group improves the adhesiveness of polyolefin resin. ing. [Problems to be Solved by the Invention] However, the improvement in adhesion of the modified polyolefin obtained by this method is still not satisfactory. In particular, the laminate obtained by adhering this modified polyolefin to metal as an adhesive has drawbacks such as being deformed by heat treatment at the baking temperature of the paint (190 to 200°C) and lacking vibration damping properties. . [Means for Solving the Problems] In view of the above-mentioned points, the present inventors have developed a polyolefin adhesive that exhibits high adhesive strength when laminated with various base materials, particularly metals, and that has good adhesive strength and high adhesive strength. As a result of intensive research in order to provide a laminate that exhibits excellent heat resistance and vibration damping properties, we succeeded in grafting polyolefin and an organic silane compound having ethylenically unsaturated bonds, and combined this modified polyolefin with specific components. It was discovered that a polyolefin composition formulated with a polyolefin composition exhibits high adhesive strength when laminated with a metal, and the laminate exhibits excellent heat resistance and vibration damping properties. The present invention was made based on the above findings, and
Contains at least three of the following components (a) to (e), and the blending ratio of each component is 10 to 95% by weight of (a) and 0 to 85% by weight of (b) in the weight of the polymer. %, (c) is 5 to 60% by weight, and (a), (b) and (c) in the total composition weight
The present invention provides a laminate consisting of a metal/adhesive polyolefin composition/metal in which the total amount of (d) is 50 to 90% by weight, and (d) is 10 to 50% by weight. Each component used in the present invention will be explained in detail below. The modified polyolefin (a) used in the present invention is obtained by grafting polyolefin and an organic silane compound having an ethylenically unsaturated bond, preferably in the presence of an organic peroxide. Examples of the polyolefins include crystalline homopolymers of propylene, binary or more block or random copolymers of propylene and other α-olefins (e.g., ethylene, butene, pentene, hexene, heptene, etc.), and dienes. Ethylene polymers such as propylene polymers, ethylene homopolymers, binary or more block or random copolymers of ethylene and α-olefins (propylene, butene, pentene, hexene, heptene, etc.) and dienes are used. Can be mentioned. Examples of the organic silane compound having an ethylenically unsaturated bond include vinyltriethoxysilane,
Methacryloyloxytrimethoxysilane, γ
-methacryloyloxypropyltrimethoxysilane, methacryloyloxycyclohexyltrimethoxysilane, γ-methacryloyloxypropyltriacetyloxysilane, methacryloyloxytriethoxysilane, γ-methacryloyloxypropyltriethoxysilane, and the like. The modifier may be used alone or in combination of two or more. Furthermore, the organic peroxide mentioned above is preferably one having a 1-minute half-life temperature of about 160 to 260°C, such as tert-butylperoxyisopropyl carbonate, di-tert-butylperoxyisopropyl carbonate, etc. Butyl diperoxyphthalate, tert-butyl peroxyacetate, 2,5-dimethyl-2,
5-di(tert-butylperoxy)hexane, 2,
5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, tert-butyl peroxylaurate, tert-butyl peroxymale acid, tert-butyl peroxybenzoate, methyl ethyl ketone peroxide, dichloride Examples include mil peroxide, cyclohexanone peroxide, tert-butyl cumyl peroxide, 2,5-dimethylhexane 2,5-dihydroperoxide, and the like. These organic peroxides may be used alone or in combination of two or more. The blending ratio of the above-mentioned polyolefin resin, modifier, and organic peroxide varies depending on the desired MFR (melt flow rate index) of the modified polyolefin, but in general, it is added to 100 parts by weight of the polyolefin resin. On the other hand, the modifier is 0.01~5
Parts by weight, especially 0.1 to 3 parts by weight, of organic peroxide
A range of 0.01 to 5 parts by weight, particularly 0.1 to 2 parts by weight is preferred. In addition, the blending ratio of the modifier and organic peroxide is
5 to 80 parts of organic peroxide per 100 parts by weight of modifier
Parts by weight ranges are preferred. The modified polyolefin used in the present invention is prepared by mixing a polyolefin resin, a modifier, and an organic peroxide by a method known per se, preferably under conditions that do not decompose the organic peroxide. The method is applied to mix the polyolefin resin, the modifier and the organic peroxide, and the resulting mixture is heated to a temperature at which the polyolefin resin melts but does not decompose, preferably about 180-260°C, especially 220-250°C.
It can be obtained by heating to a temperature of The simplest heat treatment operation is to melt and heat the mixture in an extruder at the above temperature for about 2 to 5 minutes. Further, the graft reaction may be carried out in an organic solvent. Furthermore, examples of the unmodified polyolefin resin (b) used in this invention include the polyolefin resins described above. In particular, the same type as that used to obtain the modified polyolefin is preferably used. In particular, the above-mentioned crystalline propylene polymer is preferably used as the unmodified polyolefin resin. Conventionally known additives (antioxidants, ultraviolet absorbers, etc.) may be blended with the unmodified polyolefin resin. calcium carbonate, inorganic matter,
Each modified polyolefin may be used in the form of a masterbatch of unmodified polyolefin resin. As the elastomer (c) used in the present invention, a polymer having a lower tensile modulus (ASTMD-882-73) at room temperature than modified or unmodified polyolefin polymers is used. Specifically, various polyethylenes, ethylene/propylene, ethylene/propylene/diene, ethylene/acrylic acid, ethylene/butene, ethylene/
Ethyl acrylate, ionomer, ethylene vinyl acetate, styrene/butadiene copolymers, liquid rubbers, and unsaturated acids and esters of these acids,
Derivatives such as metal salts, imides and amides, and those modified by addition with unsaturated silane compounds,
Partially crosslinked materials can also be used. Among these, ethylene/propylene/(diene) rubber or modified products thereof are preferred for crystalline polypropylene. Further, when a modified elastomer is used at this time, polyamide, polyesteretheramide, polyesteramide, polyetheramide, etc. which are compatible with the modified elastomer can be used in combination. Calcium carbonate (heavy, light) used in the present invention
(d) is preferably a powder having an average particle diameter of 0.05 to 10 μm, particularly 0.5 to 5 μm, and a specific surface area of 0.1 to 100 m ² /g, especially 1 to 30 m ² /g. Preferably, calcium carbonate is not surface-treated. Inorganic substances other than calcium carbonate used in the present invention include metals such as talc, mica, carbon black, metal powder, carbon fiber, metal fiber, silicon oxide, silicon carbonates, hydroxides,
It also includes oxides, etc., and processed and modified fibrous materials. Although these inorganic substances are not effective in improving adhesiveness, they are effective in damping vibration. Addition of electrical conductors such as metal powder, metal fibers, carbon fibers, etc. can impart electrical conductivity and enable spot welding of metal laminates (metal-adhesive-metal). In the adhesive polyolefin composition of the present invention, the blending ratio of each of the above components is (a): 10 to 95% by weight of modified polyolefin, (b): 0 to 85% by weight of unmodified polyolefin, preferably 10% by weight of unmodified polyolefin. -85% by weight, (c): 5-60% by weight of elastomer, the total of (a), (b) and (c) is 50-90% by weight of the total composition weight, (d) is
It can be obtained by mixing in amounts of 10 to 50 parts by weight. If the ratio of each component is outside the above range, the adhesiveness, heat resistance, or vibration damping properties of the resulting composition will decrease. The adhesive polyolefin composition of the present invention may contain various additives, such as weathering (thermal) stabilizers, molding aids, etc., at the time of mixing each component. The simplest mixing operation is to melt-mix the above-mentioned components in an extruder at a temperature of about 180 to 260°C, particularly 220 to 250°C, for about 1 to 10 minutes. Examples of the extruder include a single-screw or twin-screw extruder and a continuous mixer such as FCM. The effect of the present invention is further improved by performing a deaeration operation (venting) during melt-mixing. This is because there is moisture attached to the surface of the powdered inorganic substance. Next, metals used in the laminate of the present invention include iron, aluminum, copper, zinc, nickel,
Examples of metals include tin, stainless steel, brass, tin, and galvanized iron. The metal may be in the form of a plate, a plate with irregularities, or a tube, and may or may not be degreased. The method for obtaining the laminate is not particularly limited; for example, it may be formed into a film, sheet, or pellet (adhesive only) and bonded under heat, laminated outside a die, extrusion coated, or powdered. Known methods such as body painting can be used. In addition,
In lamination with metal, an epoxy resin primer may be used as primer treatment. The structure of the laminate of the present invention is basically a two-layer structure in which the adhesive polyolefin composition of the present invention and the metal described above are laminated, but various combinations can be made as necessary. For example, a combination of metal/adhesive polyolefin composition/metal is preferred;
Can be combined with paper, wooden boards, etc. Since the adhesive polyolefin composition of the present invention has high adhesive strength, it is used for coating metal plates, the inner and outer surfaces of metal tubes, copper wires, electric wires, cables, and other metals. [Example] Next, Examples and Comparative Examples will be shown. In the following description, parts indicate parts by weight, % indicates weight %,
T-peel strength, which determines adhesion, was measured in accordance with JISK6854. Heat resistance test Laminated metal plate. (25mm width, 100mm length) was processed into a V-shape with a male mold at 80 degrees, a female mold at 88 degrees, and the tip of each mold R1.
After heat treatment at 200℃ for 30 minutes, cool to room temperature and heat at 160℃ again.
After heat treatment at ℃ for 30 minutes, it was cooled to room temperature and the deformation angle was measured. Heat resistance change angle = angle after heat treatment - angle before heat treatment It is better to have little change in heat resistance. Vibration damping property The loss coefficient η was determined using the forced vibration method. Loss factor η = (f ₂ - f ₁ )/f ₀ Tensile yield point strength (adhesive) The sheet was measured using ASTMD-882-73. Example 1 Irganox 1010 (as an antioxidant) was added to 100 parts of powder of ethylene-propylene block copolymer (MFR 1.0 g/10 min, ethylene content 8% by weight, melting temperature approximately 160°C, tensile modulus 14200 Kg/m ² ). Musashino Geigy) 0.1 part, Antiox S (NOF) 0.2 part, calcium stearate 0.05 part,
0.5 parts of γ-methacryloyloxypropyltrimethoxysilane as a modifier and 0.25 parts of tert-butyl peroxybenzoate as an organic peroxide.
After mixing for 10 minutes in a Henschel mixer, melt and heat the reaction at 240℃ for 2 minutes (residence time) in a 50mmφ single-screw extruder to form modified polypropylene pellets with an MFR of about 2mmφ x 3mm for 22g/10 minutes. I got it. Calcium carbonate (Whiten SSB Red, average particle size 1.25μ, specific surface area 1.85)
m ² /g, Shiraishi calcium) and ethylene/propylene block copolymer (MFR 1.0g/10 min, ethylene content 8% by weight, melting temperature 160℃, tensile modulus
14200Kg/m ² ) of pellets (known antioxidants,
(contains calcium stearate) and ethylene/propylene copolymer rubber (Japan Synthetic Rubber)
Co., Ltd., EP-02P, tensile modulus 80Kg/cm ² ]
After blending in the proportions shown in the table and mixing in a blender, they were melt-kneaded for 2 minutes at 250°C in a 50 mmφ vented single screw extruder to obtain adhesive polyolefin composition pellets of approximately 2 mmφ×3 mm. An adhesive polyolefin sheet was prepared from this. This composition is used as an adhesive, and a degreased chrome plated steel plate (0.2 mm thick x 300 mm x 300 mm) is used as the adherend.
Using a spacer, preheat at 180 to 220℃ for 5 minutes, pressurize for 3 minutes (surface pressure of 3Kg/ ^cm2 or more), and then cool for 25 minutes (slowly cool to 50℃) to form a three-layer structure. A structural laminate board (laminate composite board) (thickness 1.0 mm) was obtained. A test piece (width 25 mm) was cut from this laminate and the adhesive strength was determined at a peeling rate of 20 cm/min. The results are summarized in Table 1. Damping property (at the primary resonance point) η (25℃) is 0.001, η
(100℃) was 0.002. Example 2 Polyethylene was used instead of EPR in Example 1 [Ube Industries, Ltd., F222, tensile modulus 1200 Kg/cm ² ]
(PE) was used. Example 3 Instead of EPR in Example 1, modified polyethylene with 0.5% maleic anhydride (polyethylene created by melt-kneading with peroxide in an extruder, tensile modulus 2819 Kg/cm ² ) (modified PE) was used. . Example 4 Ethylene/
Propylene/diene copolymer [Japan Synthetic Rubber Co., Ltd.,
EP57P, tensile modulus of elasticity 80Kg/cm ² ] (EPDM) was used. Example 5 The EPR in Example 1 was used as an ionomer [Mitsui Polychemical Co., Ltd., 1706, tensile modulus 3030 Kg/cm ² ]
I replaced it with Example 6 Talc was used as the inorganic substance. Example 7 Mica was used as an inorganic substance. Example 8 Silicon oxide was used instead of mica in Example 7. Example 9 10% nylon 6 was used instead of 10% in the modified polyethylene in Example 3. In this case, the adhesive sheet was formed and bonded at a temperature of 250°C. Example 10 The amount of EPR and carbon cal in Example 1 was increased.
These damping properties are η (25℃) 0.005, η (100℃)
It was 0.007. Example 11 Modified polyethylene, EPR, and Charcoal were used together.
These vibration damping properties are η (25℃) 0.05, η (100℃) 0.1
It was hot. Comparative Example 1 A composition was obtained in the same manner as in Example 1 except that unmodified polypropylene was used in place of modified polypropylene. The T-peel strength was 1 kg/25 mm or less.

[Table] [Effects of the Invention] As described above, the laminate made of the adhesive polyolefin composition of the present invention and metal has high adhesive strength and excellent heat resistance and vibration damping properties.

Claims (1)

[Claims] 1 Contains at least three of the following components (a) to (d), and the blending ratio of each component is 10 to 95% by weight of (a) in the polymer weight; b) from 0 to 85% by weight;
(c) is 5 to 60% by weight, and (a) and (b) are included in the total composition weight.
The total of and (c) is 50 to 90% by weight, and (d) is 10 to 50% by weight.
A laminate consisting of metal/adhesive polyolefin composition/metal. (a) Modified polyolefin obtained by grafting a polyolefin with an organosilane compound having an ethylenically unsaturated bond (b) Unmodified polyolefin (c) Elastomer (d) Calcium carbonate