JPS6320470B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an adhesion method using low-temperature vulcanization, and more particularly to an adhesion method using a rubbery polymer mainly composed of butyl rubber imparted with low-temperature vulcanizability as an adhesive. Conventionally, metal, vulcanized rubber, wood, plastic,
Pressure-sensitive adhesives that simply utilize the tackiness of rubbery polymers are used to bond similar or dissimilar materials such as glass. However, since such adhesives are made of polymeric substances with viscous flow or low glass transition temperatures, the bonded parts may shift in response to long-term stress, and furthermore, in places exposed to high temperatures above room temperature, As a result of the increased fluidity of the bonded portion, there are drawbacks such as the inability to obtain the desired adhesive force, and improvements in these have been desired. As a result of extensive research into methods for improving the adhesion of rubbery polymers mainly composed of butyl rubber, the inventors of the present invention found that by using a specific organic peroxide and a specific vulcanization aid, the adhesiveness of rubbery polymers mainly composed of butyl rubber can be improved. The inventors have discovered that when a rubbery polymer is vulcanized at a low temperature, its adhesive strength increases dramatically, and that this high adhesive strength is maintained even in a high temperature range, and the present invention has been completed. That is, the present invention uses a sheet of a rubbery polymer mainly composed of butyl rubber containing an organic peroxide (sheet A) and quinone as adhesives in an adhesive method in which an adhesive is interposed between adherends and then pressure bonded. Mainly made of butyl rubber containing at least one vulcanization aid selected from dioximes, maleimides, polyfunctional aryl compounds, polyfunctional acrylic esters, and organic metal salts with redox action. An adhesive made by gluing together a sheet of rubbery polymer (sheet B). or Sheet A is made of at least one vulcanization aid selected from quinone dioximes, maleimides, polyfunctional aryl compounds, polyfunctional acrylic esters, and organometallic salts having redox action. An adhesive made by applying or spraying a solution. or An adhesive formed by applying or spraying an organic peroxide solution onto the sheet B above. The present invention provides an adhesion method using low temperature vulcanization. The rubbery polymers mainly composed of butyl rubber used in the present invention include isoprene, isobutylene copolymer rubber, halogenated butyl rubber modified with bromine or chlorine, and isobutylene polymers, each alone or as a mixture thereof,
Alternatively, ethylene/α-olefin copolymer rubber, ethylene/α-olefin, non-conjugated diene terpolymer, styrene/butadiene rubber, butadiene rubber, butadiene/acrylonitrile rubber, chloroprene rubber, isoprene rubber, natural rubber, etc. are added to the above butyl rubber. It is made by blending.
When butyl rubber is blended with other rubbers mentioned above, if the proportion of butyl rubber decreases, properties such as airtightness, watertightness, weather resistance, ozone resistance, etc., which are characteristics of butyl rubber, will be lost, so the total amount of rubber base material will be reduced. Against
40wt% or more is preferable. Examples of the organic peroxide used in the present invention include hydroperoxide compounds such as cumene hydroperoxide and p-menthane hydroperoxide, ketone peroxide compounds such as methyl isobutyl ketone peroxide, acetylacetone peroxide, and cyclohexanone peroxide; Examples include diacyl peroxide compounds such as benzoyl peroxide. The amount of these organic peroxides used is 0.1 parts by weight per 100 parts by weight of rubbery polymer mainly composed of butyl rubber.
-20 parts by weight, preferably 1-15 parts by weight. Examples of vulcanization aids used in combination with organic peroxides include p-benzoquinone dioxime, p, p'-
Quinone dioximes such as dibenzoylbenzoquinone dioxime, N-phenylmaleimide, N,
N′-m-phenylene bismaleimide, N,N′-
p-phenylene bismaleimide, N, N'-4,
4'-diphenylmethane bismaleimide, N,N'-
Maleimides such as 4,4'-diphenyl ether bismaleimide and N,N'-4,4'-diphenylsulfon bismaleimide, diaryl fumarate, diaryl phthalate, triaryl cyanurate and triaryl isocyanurate. Polyfunctional aryl compounds, polyfunctional acrylic acids such as ethylene glycol diacrylate, trimethylolpropane triacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol methacrylate, and trimethylolpropane trimethacrylate. Examples include esters and organic metal salts having redox action such as cobalt naphthenate, ferrous chloride, and ferrous sulfate. The amount of these vulcanization aids used is based on 100 parts by weight of rubbery polymer mainly composed of butyl rubber.
It ranges from 0.1 to 10 parts by weight, preferably from 1 to 10 parts by weight. When bonding using such an adhesive component,
As adhesives, (1) a sheet of rubbery polymer mainly composed of butyl rubber containing an organic peroxide (sheet A) and a sheet of rubbery polymer mainly composed of butyl rubber containing a vulcanizing agent (sheet B); or (2) an adhesive obtained by applying or spraying a solution of a vulcanization aid to the above sheet A, or (3) an adhesive obtained by applying a solution of a vulcanization aid to the above sheet B, or Any spray adhesive may be used. When applying or spraying vulcanizing agents or vulcanizing aids, they are preferably dissolved in common organic solvents such as toluene, xylene, acetone, and methyl ethyl ketone. When the agent itself is a liquid, it can be used as is without using a solvent. Further, the above adhesive may further contain known compounding agents such as a tackifier, a filler, a softener, zinc oxide, and stearic acid factis. In particular, it is desirable to use a tackifier because it improves workability during construction. Such tackifiers include, for example, rosin resins, hydrogenated rosins, petroleum resins, and modified products thereof, and the amount used is greater than that of rubbery polymers mainly composed of butyl rubber.
It can be used in an amount of 5 to 50 parts by weight per 100 parts. In the present invention, the adhesive is interposed between adherends,
This is a low-temperature vulcanization bonding method that involves pressure bonding, but by leaving it at a temperature of 0 to 70 degrees Celsius, preferably around room temperature, for at least one day, vulcanization occurs and the adhesive strength of the bonded object increases. The surprising result is that not only is the adhesive strength significantly improved, but the high adhesive strength is maintained even in the high temperature range. Since the low-temperature vulcanization bonding method of the present invention provides such a unique effect, it can be used not only for bonding between similar or dissimilar materials such as vulcanized rubber, wood, plastics, and glass, but also for bonding between similar or dissimilar materials such as vulcanized rubber, wood, plastics, and glass. It can also be used in fields where pressure-sensitive adhesives have not been used, such as architecture and civil engineering, which require a high degree of windproofing and waterproofing, and thin vulcanized rubber fields such as waterproof sheets and rubberized fabrics. The present invention will be specifically explained below with reference to Examples. Example 1 After kneading the raw materials of each compounding composition shown in Table 1 using open rolls, they were formed into a 0.25 mm thick sheet using four calendar rolls, and this was
It was cut into 20mm x 50mm. A toluene solution of p-benzoquinone oxime was applied to the sheet with composition A, and a toluene solution of various organic peroxides was applied to the sheet with composition B, and then EPDM/butyl rubber vulcanized rubber sheets (thickness 1mm) as shown in Figure 1. These were left at room temperature (25 to 30°C), and the tensile shear adhesive strength was measured over time. The results are shown in Table 2. Example 2 A sheet made of composition A and a sheet made of composition B were prepared in the same manner as in Example 1, and after gluing them together, they were interposed between adherends and crimped as shown in Figure 1. . Store this at room temperature (25-30
℃), and the tensile shear adhesive strength was measured over time. The results are shown in Table 3.

【table】

【table】

【table】

【table】 [Brief explanation of the drawing]

FIG. 1 is a schematic diagram of an adhesive coupon. In the figure, the symbol indicates the adherend (width 20 mm), and the symbol indicates the adhesive (adhesive area 20 mm x 50 mm).

Claims (1)

[Claims] 1. In an adhesive method in which an adhesive is interposed between adherends and then pressure bonded, a sheet of rubbery polymer mainly composed of butyl rubber containing an organic peroxide is used as an adhesive (sheet A). ) and at least one vulcanization aid selected from quinone dioximes, maleimides, polyfunctional aryl compounds, polyfunctional acrylic esters, and organometallic salts with redox action. An adhesive made by gluing together a rubbery polymer sheet (sheet B) mainly made of butyl rubber. or Sheet A is made of at least one vulcanization aid selected from quinone dioximes, maleimides, polyfunctional aryl compounds, polyfunctional acrylic esters, and organometallic salts having redox action. An adhesive made by applying or spraying a solution. or An adhesive formed by applying or spraying an organic peroxide solution onto the sheet B above. An adhesion method using low-temperature vulcanization.