JPS60224B2 - Method for manufacturing adhesive composites - Google Patents

Description

[Detailed description of the invention] The present invention relates to a method of manufacturing adhesive composites.

Conventionally, in the rubber field, adhesion between elastomers and metals has been carried out by a method called vulcanization, but the rubber formulation has been devised to maintain a balance between the vulcanization rate and the adhesion reaction rate. Generally speaking, it is not possible to increase the vulcanization rate faster than that of rubber, but since it is a crosslinked type, the adhesive strength is maintained considerably when the temperature rises, but it cannot be applied dropwise to plastics.

Furthermore, plastics, such as epoxy resins and polyester resins, have extremely good adhesive strength and tensile strength with metals, but their peel strength can only reach impractical values. In the direction of this improvement, by giving flexibility to the adhesive layer, for example, by blending polyamide with epoxy resin, it is used for adhesion between metals for aircraft and can manufacturing, etc., but composites with plastic Not used for wood. For adhesion of composite materials, such as adhesion of plastic and metal, acrylic acid or its ester is generally used.
There are thermoplastic resins with carboxyl groups introduced, and ethylene/vinyl acetate thermoplastic resins for adhesion of polyester film and aluminum foil, but the peel strength at elevated temperatures significantly reduces the viscosity of the adhesive layer, so the range of use is limited. , its uses are limited.

Adhesives that exhibit practical peel strength even at elevated temperatures (up to 8,000 ℃) in adhesive-based composite materials, such as metal-to-metal or metal-to-plastic materials, and can withstand bending and scratching. There are absolutely no.

The object of the present invention is to
When heating metal, metal-plastic adhesive composite (80o
o) The objective is to provide a method for producing adhesive composites whose peel strength can be increased to the order of 2 degrees compared to conventional ones. The vinyl silane compound used in the present invention contains a hydrolyzable organic group, such as an alkoxy group such as a methoxy group, an ethoxy group, and a phthoxy group, and free radical moieties generated in the organic polymer are reactive aliphatic. Compounds having an unsaturated hydrocarbon group or hydrocarbonoxy group are suitable, and typical examples include vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltrilyacetoxysilane.

In addition, as radical generators, dicumyl peroxide, penzoyl peroxide, 2,5-dimethyl-2,5-di(
Mention may be made of organic peroxides such as tertiary phtyl peroxyhexine-3 and azo compounds such as azobis-isophthyronitonyl and dimethylazoisobutythate.

Furthermore, examples of the siloxane condensation catalyst include dibutyltin diurarate, dibutyltin dioctate, lead naphthenate, and organic bases such as ethyl amine, dibutylamine, and hexinamiso.

Plastics that can be bonded include polyolefins, that is, olefin polymers or polymers containing olefins, such as polyethylene, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers or copolymers with esters thereof, and ethylene. - Contains propylene (or gene monomer) copolymers, ethylene/phthylene copolymers, halogenated polyolefins, or those obtained by graft polymerization of vinyl chloride monomers.

Furthermore, the metals to be bonded include aluminum, copper, stainless steel, iron, zinc, tin, and alloys thereof. Note that the siloxane condensation catalyst can be added at the beginning together with the silane compound and the radical generator, or can be added at the time of molding using a masterbatch method.

Furthermore, it may be applied to a metal surface. Furthermore, the crosslinked polyolefin of the present invention may contain various additives such as antioxidants, metallurgical inhibitors, ultraviolet absorbers, and colorants that do not impede the effects of the present invention. Next, examples of the present invention will be described together with reference examples.

Reference example 1 Specific gravity 0.88, ethylene content 80%, melt viscosity index 1
, ZP (190oo) of highethylene copolymer,
Vinylmethoxysilane 2Phr, Dikymyl peroxide 0. Sahr, dibutyl tin diurarate 0.01
The admixture formed by adding phr to surface-clean copper (0.1
Sandwiched between a sheet (willow thickness) or an aluminum (0.2 rib thickness) sheet and a polyethylene sheet, and heated to 10k9 at 160℃.
' (gauge pressure), 100 qo after heating and pressurizing for 10 minutes.
100% R rule, contact for 4 hours and crosslink, and metal ~
Polyethylene bonding was performed.

Example 1 Specific gravity 0.8 & ethylene content 80%, melt viscosity index 1
．． 2y/min (19000)/yetlene-propylene copolymer 5, specific gravity 0.95, vinyl acetate content 28%, melt viscosity index 6. Five parts of ethylene/vinyl acetate copolymer at a rate of 190 oo/min (190 oo) were uniformly melted and mixed into a single body, and to this was added 0.0 ml of vinylmethoxysilane and 0.0 ml of dikymyl peroxide. Adhesive film is made by adding 0.03 phr of dibutyl tin diurarate, copper (0.1 leg thickness), aluminum (0.2 willow thickness)
, scissors "16000, 10k" between the stainless steel (0.4 rib thickness) sheet and the 1 willow thick polyethylene sheet, respectively.
g' (gauge pressure), 100 qo after heating and pressurizing for 10 minutes
, 100% R rule was brought into contact for 4 hours to effect crosslinking and adhesion.

Example 2 Specific gravity 0.9, vinyl acetate content 28%, melt viscosity index 6
．． 0 gr/min (190oo) of vinyl acetate copolymer,
Vinyl methoxysilane (masu hr), dicumyl peroxide (0.2 phr), and dibutyl tin diurarate (0.01 phr) were added to make an adhesive film.
Sandwiched between aluminum (0.3 skin thickness), copper (0.1 skin thickness) sheets and 1 rib thickness polyethylene sheet,
After heating and pressurizing with 160qo, 10kg/c liquid (gauge pressure) for 10 minutes, it was kept in contact with 100oo, 100% RH for 4 hours and bonded.

Example 3 Specific gravity 0.94, vinyl acetate content 19%, melt viscosity index 2
．． 5 (19000) vinyl acetate copolymer, vinyl methoxysilane (Book 11r), dikymyl peroxide (0.Shr), dibutyl tin diurarate (0.01
phr) to make an adhesive film, sandwiched between an aluminum (0.2 skin thickness) sheet and a willow polyethylene sheet, 16000, 10k9' (gauge pressure),
Bonding was carried out for 1 minute.

Based on the above example, the sample was tested in 25 pigs at a tensile rate of 200 ribs/
I performed the 18-year-old test in minutes.

The testing machine is a 106 type tensile testing machine (with constant temperature bath) manufactured by Uejima Seisakusho.

The results are shown in the table below.

[Unit of peel strength: K9/25 side medium] As described above, the present invention is not only unique in that it has achieved a peel strength at elevated temperatures that was previously unattainable, but also
This will further expand the utility value and range of applications of adhesive composite materials.

Claims (1)

[Claims] 1. Melt viscosity index of 1.5% with vinyl acetate content of 10-30%.
A vinyl silane compound of 0.5 to 3.0 ph is added to the ethylene/vinyl acetate copolymer at 0 to 6.0 gr/min (190°C).
r, a silane graft polymer obtained by adding 0.05 to 0.3 phr of a radical generator and heating is provided on a metal surface, heated and pressurized, and then brought into contact with moisture in the presence of a siloxane condensation catalyst. Method of manufacturing adhesive composites. 2 Melt viscosity index 1.2 with vinyl acetate content of 10-30%.
Ethylene/vinyl acetate copolymerization at 0 to 6.0 gr/min (190°C) and a melt viscosity index of 0.0 with an ethylene content of 80%.
A mixture of 2 to 1.5 gr/min (190°C) high ethylene/propylene copolymer, 0.5 to 3.0 phr of a vinyl silane compound, and 0 radical generator.
．． 05 to 0.3 phr and heated to obtain a silanda raft polymer is provided on a metal surface, heated and pressurized, and then brought into contact with moisture in the presence of a siloxane condensation catalyst. .