JPS5914072B2 - Extrudable adhesive and its manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is a solid at room temperature and has a rubber weight of 40 to 79 mm. ,
Carbonaceous filler 4 to 30 weight? , silica filler 4-30% by weight, non-reactive phenol condensate and/or resin 4-30% by weight
20 weight? , thermoplastic aliphatic hydrocarbon resin 4 to 20 weight? and an extrudable adhesive containing 0.03 to 4% by weight of a lubricant.

The adhesive of the present invention is useful for applying to a substrate, such as a tape, by extrusion through a wide slit nozzle;
It may also be manufactured in a form suitable for coextrusion with a carrier. Adhesives of great industrial importance are applied to a support, which can be a tape or any other material to which an adhesive layer is applied.

Generally it is necessary to obtain a uniform layer. This is a difficult task that is influenced to a large extent by the physical state of the adhesive during application to the support. Generally speaking, solutions in solvents were believed to produce favorable physical conditions for applying a uniform, sticky layer of adhesive material on a support.

The technique of applying adhesive to a substrate from a solvent solution is referred to as solution coating. Solution coating has become a highly developed method. Solution coating methods have been developed despite significant drawbacks associated with the volatile organic solvents used in this type of process. Many commonly used solvents are flammable, form explosive mixtures with air, or are toxic to humans. After applying the adhesive layer, the solvent usually has to be removed from the layer. In high-speed mass production processes, the coated support is left unattended and
It is not possible to wait for the solvent to evaporate. Additional costs are typically incurred to facilitate solvent removal with hot air, infrared radiation, or other accelerated evaporation methods. Economic and environmental protection needs
Frequently, solvent recovery is required, and the equipment and manpower to meet these requirements imposes another cost burden on this method. Because of the aforementioned drawbacks, significant efforts have been made to find alternatives to solution coating.

Research has primarily focused on two approaches: replacing the solvent with water or applying the adhesive in the molten state, generally without water or solvent. When the solvent is replaced by water, the adhesive is usually in a physical state such as a suspension, emulsion, or dispersion.

These aqueous systems overcome the problems of flammability, explosion hazards and toxicity hazards. However, as with solvents, it is necessary to remove the water. Unfortunately, water evaporates more slowly than normal solvents, requiring longer, more expensive, and time-consuming drying steps. The aqueous system is
Furthermore, they have the disadvantage of being limited in their ability to wet the desired support, especially the synthetic resin support, which is of greatest industrial importance, and to form a uniform layer. Hot melt adhesives, ie adhesives that are applied to a substrate in the molten state, do not have the hazards of solvents and the drying requirements of solvent-based and aqueous systems, unlike solutions, suspensions, emulsions or dispersions.

Hot melt adhesives are generally applied at temperatures of about 120-200C, preferably about 135-1851C. This creates drawbacks that do not normally occur in solvent-based or aqueous systems. Prolonged heating of the adhesive material during the hot melting process can lead to decomposition of the adhesive components, clogging of application equipment, and uneconomical work interruptions. Furthermore, these rather high application temperatures
There is a tendency to deform the plastic sheet normally used as a support, so that the sheet does not retain its true dimensions. Additionally, due to their thermoplastic nature, conventional hot melt adhesives are sensitive to subsequent temperature effects or stresses, which can significantly impair the performance of the adhesive. Although significant efforts have been made to perfect aqueous and hot melt application systems, methods of applying adhesives from solvent solutions have proven to have significant drawbacks.

The fact that a complete solution has not yet been found is evidenced by the fact that solvent solutions are still an important element in the adhesive application industry. Accordingly, there is a need to have improved adhesive compositions and improved methods of applying them to articles and substrates. The invention is based on the discovery of adhesive compositions that are solid at room temperature and can be extruded in the solid state.

The composition of the present invention comprises (a) about 40-79% rubber; (b)
Carbonaceous filler approximately 4-30%, (c) silica filler approximately 4-30%
30%, (d) Zinc oxide about 2-8%, (e) Oil about 2-1
0? , (f) about 4-20% non-reactive phenol condensate;
(g) about 4-20% thermoplastic aliphatic hydrocarbon resin; and (h) about 0.3-4% lubricant (each percentage by weight). The invention also relates to a method of applying the composition in the solid state to a support, for example by extruding it onto a pre-processed thermoplastic support through a wide slit nozzle at room temperature or above.

It is also possible to coextrude the support and a suitably formulated adhesive at slightly elevated temperatures. For example, the support and the adhesive according to the invention may be extruded through a two-layer wide slit nozzle;
Or, preferably, a variation of the conventional inflation method can be used, in which the adhesive is extruded simultaneously into the interior of the tubular film by means of a two-layer annular nozzle. Other aspects of the invention include advantageous embodiments of the invention detailed below.

The adhesive composition of the present invention is in a solid state.

Advantageously, the adhesive composition of the present invention contains almost no components boiling below 100° C. at 760 mmHg;
Some ingredients may contain residuals or traces of liquids that boil below 100°C. If the composition contains more than a trace or residual amount of liquid, it is either insufficient to convert the composition into a substantially solid state, or it significantly interferes with extrusion of the composition. A variety of rubbers, fillers, oils, phenolic condensates or resins, aliphatic hydrocarbon resins, and lubricants may be used in the practice of this invention. Thus, for example, the availability of different rubber materials makes it possible to adapt the properties of the adhesive according to the invention to specific applications and/or support materials. Similarly, the availability of various carbonaceous fillers, silica fillers, zinc oxide fillers, oils, phenolic resins, aliphatic hydrocarbon resins, and lubricants allows for a variety of choices.
It is possible to customize or adapt the composition for specific applications. However, particularly advantageous results are obtained with the following advantageous components. (a) Rubber component The rubber used in the present invention is butyl rubber, particularly preferred butyl rubber is 95 to 98% by weight of isoptylene having a degree of unsaturation of about 1.5 to 2.0 mol %. and isoprene 2-5
weight? It is a copolymer with

Non-rubber materials included in the rubber mixture include polyterpene resins (e.g. PiccOlyt® 2).
e) Coumaron-indene resins (commercially available as "Neville" resin), modified rosins, rosin esters, pentaerythritol esters, ester rubbers (e.g.
There are also commercially available resins such as ``nsOl'' resin.

Adhesive resins of this type are well known to those skilled in the art of pressure sensitive adhesives. These, in accordance with recognized principles, generally have an affinity for the support, with a view to obtaining a homogeneous blend which has dry tack to the material to which the support is to be bonded by means of an adhesive. Mixed with rubber. Rubbers, including blends of rubbers and rubbery mixtures of rubber and non-rubber materials, are tacky, unvulcanized solid rubbers that are activated by curing agents during or after application of the adhesive layer to the substrate. Or a vulcanizing agent may be present. Advantageously, the rubber itself has a mu viscosity of about 50 to about 80 at +100°C.
Although the composition may contain any amount of rubber in the range of about 40-79%, the optimum percentage of rubber is 57.48% when using the preferred butyl rubber copolymers described above.

(b) Carbonaceous Filler Component A preferred carbonaceous filler is carbon broccoli, about 30%
It may be an acetylene black, a channel black, a thermal black, or a furnace black with a surface area of ~150 rr1/g.

Generally, commercially available carbon blacks have small particle sizes that are well suited for the practice of this invention. however,
If the carbon black is supplied in the form of pellets which do not readily redisperse when kneaded with the rubber in a Banbury mixer, for example, it is necessary to crush the pellets before mixing them with the rubber. Particular preference is given to using activated acetylene or furnace carbon blacks.

Carhop racks may use any amount of carbon black in the range of about 4-30%, but when using the preferred carbon black, the optimum amount is 9.345%.
(c) Silica Filler Component The silica may be naturally occurring or synthetic in the form of a fine powder with a surface area in the range of about 20 to 200 m2/9.

It has a molecular composition for the formula SiO2 and is approximately equal to said composition whether SiO2 is present alone or in a mixture with other materials that do not significantly impair its functionality or the performance of the adhesive composition. Contains substances. However, preference is given to amorphous synthetic silica powders or precipitates produced by precipitation or pyrogenic methods.

For example, such powders are produced by vaporizing silicon oxide at 2,000'C or by reducing the dioxide at 1,700C to produce silicon monoxide. This silicon monoxide is oxidized in situ using a conventional method to obtain fine amorphous silica. In another known method, silicon tetrachloride is combusted in hydrogen and the finely divided product is collected on a cold surface. The resulting product is characterized by a very fine particle size, more than 99% of which passes through a 325 mesh sieve. Particular preference is given to using activated silica.

Any amount of silica in the range of about 4-30% may be used, but when using activated silica, the optimum amount is 9.345%. 1) Zinc oxide component Very finely divided zinc oxide is advantageous.

More than 99% should pass through a 10,000 mesh/~ sieve.

It is particularly advantageous to use activated zinc oxide having an average particle size of about 25 to 100 microns, especially about 50 microns. Any enemy zinc oxide in the range of about 2-8% may be used, but when using the preferred active zinc oxide, the optimum amount is about 3%.
．． It is 738%. -.) Oil The component oil may be any light oil, natural or synthetic, having a viscosity of about 70 to 90 centistokes at +20°C.

Light paraffinic mineral oils with a content of aromatics not exceeding about 10% are particularly advantageous. ``) Phenol condensation component The phenolic condensation component used in the present invention includes substituted or unsubstituted phenol compounds, including monovalent or polyhydric phenols, and aldehyde compounds reactive with the phenol compounds (formaldehyde, other aldehydes, etc.). and an aldehyde donor or precursor).

It can be prepared from any phenolic compound and any aldehyde compound or any mixture of such compounds, with or without another modifier, as long as the criteria described below are met. The phenol aldehyde condensate is produced from a viscous liquid condensate to about 120% by the ball and ring method.
It should be in the form of a resinous solid with a softening point up to °C.

This material should be non-reactive. That is, it does not substantially react with other components of the composition under the conditions of manufacturing the adhesive composition and the conditions of application to the support. Generally, any degree of reaction that significantly impairs the extrudability or adhesion of the composition is considered substantial. The resin used is therefore of the thermoplastic type. For this reason, the condensate or resin has a methylol content of not more than about 1%, for example about 0.3-1%. This type of condensate has no latent thermosetting properties. Unmodified and modified phenolic aldehyde condensates are known which can improve the tack retention, reduce the apparent viscosity or increase the adhesive and cohesive properties of adhesives.

Generally these are oil-soluble thermoplastic phenolic resins. Known modified phenolic resins conventionally used for this type of purpose include, for example, phenol-modified coumaron indene resins, furfureruf enolic resins and terpene-modified phenolic resins, such as acidic condensation of terpene hydrocarbons or alcohols with phenols; It is produced by subsequently converting the substituted phenol into a resin by contacting it with formaldehyde. All phenolic aldehyde components may be viscous liquid condensates or resinous solids or materials of intermediate consistency, such as those referred to as semi-solids.

Mixtures of the aforementioned can be used. however,
The most advantageous material is an oil-soluble condensate of phenol and formaldehyde, which is solid at room temperature (2'C), has a softening point of about 80-120C, and has a concentration of about 0.3-1.0%. It is a thermoplastic resin-like material with a methylol content. The composition may contain any amount of phenol aldehyde condensate or mixture of condensates ranging from about 4 to 20%, but the optimum amount when using the preferred phenol aldehyde resins described above. is 9.813%. (g) Thermoplastic aliphatic hydrocarbon resin component This component is approximately +70 to +110 by the ball and ring method.
It may be any resinous, primarily aliphatic oligomer or polymer having a softening point of .degree.

This generally applies, for example, to the homopolymerization or copolymerization of unsaturated hydrocarbons having from about 2 to 8 carbon atoms (including mixtures of unsaturated hydrocarbons having an average number of carbon atoms per molecule in this range). Therefore, it is manufactured by a known contact method.
The most preferred resins consist of one or more polymerized olefins, primarily (greater than 50%) C5 olefins alone or in mixtures with other olefins that can be polymerized with about 1,5
It is an aliphatic hydrocarbon resin having a molecular weight of 0.00. Approximately 4
Any amount of thermoplastic aliphatic hydrocarbon resin can be used in the range of -20%.

However, it mainly contains C5 olefin, and about 1,500
The optimum amount is believed to be 7.009% when using a preferred resin having a molecular weight of .

(h) Lubricant Component The lubricant can be any lubricant that is compatible with the remaining components of the mixture.

Regarding this substance, 2 lubricant 2 herein indicates that it is preferable to use a substance that can function as a lubricant when the mixture is extruded in the solid state. Known lubricants which are solid at room temperature are, for example, metal stearates, such as calcium and zinc salts; fatty acid amides and esters, such as ethylene bisstearamide; fatty acids, such as stearic acid and hydrocarbon waxes. Increasing the amount of this type of lubricant serves to reduce the melt viscosity if it is too high. Lubricants having a melting point of about 200°C are advantageous;
Stearic acid is the best. Any amount of lubricant ranging from about 0.3 to 4% may be used, but about 0.467% is optimal when using the preferred stearic acid. The composition is a generally tacky, homogeneous mixture that flows smoothly enough to form a flat, uniform film when extruded through a wide slit nozzle.

The mixture consists essentially of the above-mentioned components and may contain significant amounts of additional substances, but no additional substances should be present which would impair the above-mentioned properties of the composition. The amounts indicated in the present invention and? are all by weight, component (a)
The weight percentages of (h) are based on the total weight of components (a) to (h). If additional substances are present, they may be included in the above criteria depending on whether they are present as a substitute for or in addition to components (a) to (h). However, it does not have to be included. The resulting composition is about 3~
An example having a melt index of 23 and characterized by moderate to excellent cohesiveness and acceptable to excellent extrusion performance is described below. Thus, the composition as a whole has a melt index ranging from about 3 to 23, preferably from about 5 to 201, particularly preferably from about 10 to 20. The standard technique for measuring melt index is AST.
It is described in the M standard Dl238-70, which is about 3
．． 04kg/? The flow rate (melt index) is measured by an extrusion plastometer at 190° C. using a piston load of (approximately 43.251 b/In2).
The melt index is expressed as the number of 9 cutlets extruded per minute after discarding the first two cuts taken 5 minutes after the start of extrusion and 1 minute thereafter. The compositions of the invention are prepared in any suitable mixing equipment, especially rubber kneading equipment, such as a Banbury mixer.

It is particularly advantageous to mix the ingredients by adding them in stages during thorough kneading at a temperature in the range of about 90 DEG to 200 DEG C. For example, most or all of the rubber and silica can be thoroughly mixed and kneaded before adding the zinc oxide. In a preferred operation described below, at least one part of the carbonaceous filler, the phenolic condensate and the hydrocarbon resin is added before adding the zinc oxide. Advantageously, the addition of the oil is part of or follows the final addition of the phenolic condensate and/or hydrocarbon resin. Therefore, in an advantageous method, the entire amount of rubber is first introduced into a punched dispersion kneader.

The dispersion kneader is first heated to a temperature of about 90-110°C. The rubber is kneaded and ground under these conditions for about 2-3 minutes.
Intermittently, half of the silica is added at a temperature of about 130°C and the mixture is subsequently kneaded for about 3-5 minutes. Approximately 130-140℃
Add the remaining silica and then heat the mixture at a temperature of about
Mix for 5 minutes. About half of each of carbon black and two types of resin (phenol-formaldehyde condensate and thermoplastic hydrocarbon resin) are added to a mixture at about 160 to 170°C, and the mixture is then kneaded for about 3 to 5 minutes. .
The remaining carbon black is added along with all of the zinc oxide, the mixer contents are brought to a maximum temperature of about 180 DEG-200 DEG C., and the mixture is kneaded at this temperature for about 5-10 minutes. The balance of the two resins and the entire amount of mineral oil are added at about 180-200°C and the mixture is kneaded for about 3-5 minutes.

The mixture is cooled to about 160-170°C, stearic acid is added and kneaded for an additional 3-5 minutes. The finished adhesive or binder is removed from the equipment, placed in a suitably processable form, and allowed to cool. Because of the inherent tackiness of the adhesive or binder composition, it is recommended that it be in a specially processable form that can be advantageously handled and processed.

For example, this objective is achieved by removing the binder or adhesive composition from the production vessel or kneader by a suitable conveying mechanism, such as a feed starch, and conveying it to the extruder. The extruder forms the binder into ropes or strips which, upon exiting the extruder, are surrounded by a separating layer. This layer may be a thin film of polyethylene, for example. In some cases, the rope or strip with the separating layer is wound up, for example onto a roll. In addition, the binder is made into granules,
It can be stored in granule form until use. The ropes, strips or granules of adhesive or binder produced in the above process can be fed to an extruder to coat or impregnate tapes or other supports.

With an extruder having a wide slot nozzle, the adhesive composition can be applied, for example, by extrusion coating onto pretreated substrates, for example thermoplastic substrates. A two-layer wide slit nozzle can also be used to co-extrude the thermoplastic resin support and the adhesive composition of the present invention.
A particularly advantageous method is to use a two-layer annular nozzle and extrude the thermoplastic resin support through the annular nozzle by the inflation method. A nozzle of this type with two concentric orifices can extrude the thermoplastic tubular body through one orifice and the adhesive of the invention through the other orifice, thereby allowing the support and its one
An adhesive layer that adheres to both surfaces can be formed at the same time.

According to the accepted principle of coextrusion, two parts are extruded at the same time.
The seed materials are extruded at the same temperature range, are fairly close in extrusion viscosity, and are formulated so that they stick together.

Therefore, when the compositions of the present invention are used in a coextrusion process, the melt index of the composition is adjusted so that the melt index is in the range of about 3 to 23 at the temperature at which the coextrusion is carried out. It is advantageous for the extrusion viscosity of the adhesive mixture to be fairly close to that of the melt from which the support film is extruded. These adjustments are made by increasing or decreasing, respectively, the molecular weight, viscosity, and relative amounts of the components according to established principles of extrusion blend formulation. An advantageous use of the adhesives or binders of the invention is in the coating (including impregnation) of adhesive tapes.

Adhesive tapes are strips of thin, flexible substrates such as paper, cellophane, plastic, cloth, etc., usually in rolled form. For example, tapes of this type are used to seal cracks, bond plywood, seal containers such as tanks, fasten medical bandages, protect or insulate electrical wires, and the like. A particularly advantageous use of the binder according to the invention is as an adhesive for adhesive tapes used as corrosion protection on metal pipes for conveying gases such as oil or natural gas. The support coated with the adhesive according to the invention adheres directly to the working surface. The bonding agent of the present invention is a pressure sensitive adhesive that adheres to a wide range of materials by simply placing the adhesive on a working surface and applying pressure. However, if a stronger adhesive bond is desired, a primer can be applied. Application of a primer is also useful in providing a more effective barrier layer, for example for insulation purposes. A simple way to make a suitable primer that is compatible with the adhesive is to mix the primer with a solvent and optionally additional resins and/or rubbers.

For example, the primer may contain about 15 to 3
0%, about 65-75% gasoline, such as 80-110 octane, and about 4-10% thermoplastic hydrocarbon resin. As another example, about 5-15% binder, about 83-90% chlorinated hydrocarbon solvent, such as methylene chloride.
and about 2-5% thermoplastic hydrocarbon resin. Advantageously, the hydrocarbon resin is of the same type as the hydrocarbon resin used in the binder. The primer composition currently considered optimal is 26.516% binder according to the invention, 8
68.184% by weight of 0-110 octane gasoline and the same thermoplastic aliphatic hydrocarbon resin (predominantly containing 5 carbon olefins, molecular weight about 1500, softening point about 70 to 11 'C).

The adhesive compositions of the present invention have one or more, usually some, and advantageously all of the following advantages. The main, essential advantage of the composition is its extrudability. This depends, in part, on the type and amount of filler used. A homogeneous adhesive can be produced from the composition according to the invention. This makes it possible to produce a roll of adhesive tape that has excellent adhesive properties and is easily unwound without leaving any adhesive on the back side. The present invention provides an adhesive with balanced stability, adhesion and processability. The present invention makes it possible to produce adhesive tapes that are highly resistant to plastic deformation stimulated by mechanical or thermal factors and yet have excellent extrusion and adhesive performance. For example, in accordance with the present invention, a plasticized polymeric film, such as a vinyl chloride or vinyl chloride monoacetate film, is coated thereon and is stabilized in permanent balance with the film support. Dry tack pressure sensitive adhesives can be produced that yield a tape structure. Further, according to the present invention, the binder has extremely low gas permeability, excellent light resistance, oxidation resistance, and ozone resistance, good permanent bending resistance, and excellent mechanical properties such as rebound resistance. can be manufactured. The composition, when intimately and homogeneously mixed, exhibits cross-linking or network-like properties between the filler particles;
It clearly develops a special structure that favors the extrusion performance. It is clear that optimum extrusion performance is obtained when using the advantageous manufacturing method described above. Next, the present invention will be described in detail based on Examples, in which all "parts" represent "parts by weight" unless otherwise specified. Example 1. As shown in column 1 of Table 1 below, 40 parts of butyl rubber, 6 parts of activated zinc oxide, 13 parts of activated silica, 20 parts of acetylene black, 9 parts of mineral oil, 4 parts of hydrocarbon resin, 4 parts of stearic acid, and 4 parts of phenolic resin. parts (all corresponding to particularly preferred forms of these compounds as described above) are mixed by means of the preferred kneading operations described above.

The resulting composition, with a melt index of about 23, exhibits above average extrusion performance, but only mild cohesive performance. Example 2. The same ingredients used in Example 1 were mixed according to the procedure of Example 1 in the proportions shown in Table 1, column 2.

The resulting adhesive has a melt index of approximately 15;
It exhibits excellent extrudability, has very good molding properties and adhesion properties, and is particularly suitable for the production of adhesive tapes. Example 3
．． Additional adhesives were prepared using the ingredients and procedures of Example 1 in the proportions shown in Table 1, column 3.

This adhesive has a melt index of about 7 and exhibits good extrudability and good molding properties. Example 4. Using the ingredients and procedures of Example 1, using the proportions shown in Table 1, column 4, an adhesive composition was produced having a melt index of about 6 and properties similar to the product of Example 3.

Example 5. Using the materials and procedures of Example 1 and the proportions shown in Table 1, column 5, an adhesive with a melt index of about 3 was prepared.

It has acceptable extrudability but excellent flocculation performance. The adhesive obtained in Example 2 was used to make an adhesive tape and tested for peel strength (peel resistance) according to the method described in German Industrial Standard (DIN) 30672. Method After removing sweat compounds from the surface of the tube, the tube surface and adjacent coatings are primed with a primer consisting of the adhesive from Example 2.

After the predetermined evacuation time, this pipe has a thickness of 0.3 m77! An adhesive tape coated with 0.2 mm of the adhesive obtained in Example 2 is wrapped around a polyethylene sheet so that the tape surface overlaps by 50%, and an additional thickness of 0.5 m77 is applied for mechanical protection. It was wrapped with a roll sheet and fixed with adhesive tape. The system was subjected to temperatures up to 50° C. and adapted to the polyethylene coating. Test 1. Test DI of corrosion protection strips and substrates as supplied
Tests were carried out in accordance with the items 5 and 4 of Chapter 5 of N3O672.

The results are shown in Table 2 in comparison with standard values. 2. Testing of Tube Coatings Tests of tube coatings were carried out according to DIN 3 O 672 Chapter 5, 5, 5, Requirement B and the results are reported in Table 3 in comparison with the required values.

Results As is clear from the results in Tables 2 and 3, it can be said that the adhesive of the present invention has strong adhesive strength that satisfies the DIN3O672 standard.

Having thus fully described the invention and its various advantageous embodiments, certain features will now be described in further detail.

The following description generally concerns the function of each component in the mixture and the physical relationships between the individual components.

The substrate of the whole mixture is the above-mentioned rubber, in particular 1.5-2.0 mol%
of unsaturation and a viscosity of 50 to 80 μm at +100°C. The butyl rubber is almost non-reactive in the total mixture, due to its very low degree of unsaturation. Only rubbers that are as resistant to aging as possible should be used, such as in the case of butyl rubber. Natural rubber and other synthetic rubbers can be used, butyl rubber being preferred. Carbon black and silicon dioxide fulfill the same function in the overall mixture. Firstly, they enhance cohesiveness, and secondly, carbon black has a coloring effect. Silicon dioxide is active silicon dioxide produced by a precipitation method or a thermal decomposition method, having a surface area of 20 to 200w1/9, and existing in an amorphous state. Advantageously, the carbon black is an activated acetylene carbon black or a furnace carbon black having a surface area of about 30 to 150 Tr1/9. The zinc oxide is rubber,
It is particularly useful for preventing undesirable decomposition reactions of butyl rubber. The mineral oils mentioned primarily have the function of softeners and thus at the same time increase the inherent tack and serve to increase the tackiness of the mixture. The resins, namely the phenol-formaldehyde condensate and the thermoplastic aliphatic hydrocarbon resin, serve to create the inherent tackiness of the entire mixture. Said fatty acids, especially stearic acid, serve as a lubricant during the production and processing of the entire mixture. The following applies to each of the three types of solid fillers mentioned above; the term "active" refers to the reactivity with which the filler can participate in the solid state in reactions that in the present case primarily increase cohesiveness. It means having the center on its surface.

The surface area was measured by the BET method (nitrogen absorption according to the Brunnauer, Emmet and Teller method).

This method is ``7 Urmans Encyclopedia 1.
Ullmanns En
zyklOpKdledertechnischenC
hemie) Volume 2/1 (Urban and Schwarzenberg, Milunchen, Berlin), 1961, pages 754 et seq., especially pages 758. For lead oxide, the sieve fineness was shown (99 weight? or more is 10,000
mesh/Cd (:!) passes through the sieve).

The sieve fineness of the other two solid fillers is not critical. This is because there are dichotomous particles, that is, aggregates. According to the invention, carbon black may be used in the form of pearls if desired. The carbon black is hydrophobic.

The other two fillers mentioned above, silicon dioxide and zinc oxide, are hydrophilic. The following description relates to phenol-formaldehyde condensates.

This product is a so-called 2-novolak type 2 resin, i.e., the nonvolatile compound formed when heating phenol and formaldehyde in a ratio of 2:1 to 1.6 in the presence of an acid (tartaric acid, hydrochloric acid, dilute sulfuric acid, acid salts). It is a curable, permanently meltable, alcohol-soluble and toluene-soluble phenolic resin.
The mu[me] viscosity was measured with a mu[me] viscometer (apparatus and method described in 2 Ullmans Encyclopedia der Technitzien Hemi 1'' 9 vol., Urban and Schwarzenberg, Millenchen, Berlin). , 1957 40
(page 8).

The Furnes carbon black was made by the Furnes method (apparatus and method described in 1 Ullmans Encyclopedia der Technissien Hemi 1, vol. 14, Urban and Schwarzenberg, Milunchen, Berlin, 1963). 799 pages).

The definition of the melt index is given in Ullmans Encyclopedia der Technicienchemi, Vol. 14 (Urban and Schwarzberg, Milunchen, Berlin), 1963, p. 156.

The punched dispersion kneader for the production of adhesives operates on the Banbury mixer principle.

The dispersion kneader used in the present invention is operated by compressed air and has punches that prevent the mixture material from escaping upwardly from the kneading chamber. The wings are placed on the horizontal plane. The mixing of the materials in the kneader is extremely intensive. This is because the material is mixed between the blades and especially between the tank wall and the blade. Having thus described the invention and various advantageous embodiments thereof, those skilled in the art may make modifications not specifically described that fall within the scope of the invention.

Claims (1)

[Scope of Claims] 1 Mainly: (a) 40-79% butyl rubber (b) 4-30% carbonaceous filler having a surface area of about 30-150 m^2/g (c) about 20-200 m^2/g silica with a surface area of 4-30% (d) 99% or more of 1
Zinc oxide 2~ passed through a sieve of 0,000 mesh/cm^2
(e) 2 to 10% oil having a viscosity of about 70 to 90 centistokes at 20°C; (f) a liquid concentrate to resinous solid consistency at 20°C;
4-20% (g) of a non-reactive condensate of a phenolic compound and an aldehyde compound, having a softening point of up to
4-20% thermoplastic aliphatic hydrocarbon resin with a softening point of 110°C (h) 0.3-4.0% lubricant solid at 20°C
An extrudable adhesive, characterized in that the percentages of components (a) to (h) are percentages by weight relative to the total amount of components (a) to (h) in the adhesive. 2 95-98% by weight of isobutylene with a degree of unsaturation of 1.5-2.0 mol% and a Mooney viscosity of 50-80 at 100°C
57.480% by weight of butyl rubber consisting of a copolymer of 2 to 5% by weight of isoprene; 9.345% by weight of activated acetylene black or furnace black having a surface area of approximately 30 to 150 m^2/g; by precipitation method or high pyrolysis; Manufactured, surface area 20-2
00m^2/g active silicon dioxide 9.345% by weight with an average particle size of about 50mμ and more than 99% by weight 10,00
Activated zinc oxide passing through a 0 mesh/cm^2 sieve3.
738% by weight aromatics content up to 10% by weight and +
2.803% by weight mineral oil with a viscosity of 70-90 centistokes at 20°C. Non-reactive and non-thermally reactive phenol with a methylol content of about 0.3-1.0% by weight.
Formaldehyde condensates or corresponding phenolic resins with a softening point of about 80-120°C, containing mainly 9.813% by weight C5 olefins, with a molecular weight of about 1,500 and a softening point of 70-110°C The adhesive according to claim 1, comprising 7.009% by weight of a plastic aliphatic hydrocarbon resin and 0.467% by weight of stearic acid. 3 Mainly: (a) 40-79% butyl rubber (b) 4-30% carbonaceous filler with a surface area of about 30-150 m^2/g (c) silica with a surface area of about 20-200 m^2/g 4-30% (d) 99% or more is 1
Zinc oxide 2~ passed through a sieve of 0,000 mesh/cm^2
8% (e) Oil having a viscosity of about 70-90 centistokes at 20°C 2-10% (f) A liquid concentrate to resinous solid consistency at 20°C, which resinous solid has a viscosity of about 120°C
4-20% (g) of a non-reactive condensate of a phenolic compound and an aldehyde compound having a softening point of up to 70-1
Thermoplastic aliphatic hydrocarbon resin with a softening point of 10°C 4
~20% (h) Consists of 0.3 to 4.0% of a lubricant solid at 20°C, where the percentage of components (a) to (h) is the sum of components (a) to (h) in the adhesive. To produce the adhesive, which is a weight percent of the amount, first the total amount of rubber is
The rubber was kneaded into powder under these conditions for about 2 to 3 minutes, then half of the silicon dioxide was added at 130°C, and the mixture was kneaded for an additional 3 to 5 minutes. , then the remaining silicon dioxide was added at 130-140°C, the mixture was kneaded for another 3-5 minutes, the mixture was heated to 161-170°C, and carbon black and two resins (phenol-formaldehyde condensate and thermoplastic hydrocarbon resin)
Add half of each, knead the mixture for another 3 to 5 minutes,
The total amount of remaining carbon black and activated zinc oxide was reduced to 18
The mixture was kneaded for an additional 5-10 minutes, then the remaining half of both resins and the entire amount of mineral oil were added at 180-200°C.
Add at 200 °C, knead the mixture for another 3-5 minutes, reduce the temperature of the mixture to 160-170 °C, then add stearic acid, knead the mixture for another 3-5 minutes, and finally A method for producing an extrudable adhesive, characterized in that the adhesive is discharged from a device, put into a processable form, and cooled.