CA1224396A - Solution welding material and process for solution welding of plastics shaped bodies - Google Patents
Solution welding material and process for solution welding of plastics shaped bodiesInfo
- Publication number
- CA1224396A CA1224396A CA000417772A CA417772A CA1224396A CA 1224396 A CA1224396 A CA 1224396A CA 000417772 A CA000417772 A CA 000417772A CA 417772 A CA417772 A CA 417772A CA 1224396 A CA1224396 A CA 1224396A
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- CA
- Canada
- Prior art keywords
- synthetic resin
- solvent mixture
- solution
- process according
- volume
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
- C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
- C08J5/125—Adhesives in organic diluents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/01—General aspects dealing with the joint area or with the area to be joined
- B29C66/05—Particular design of joint configurations
- B29C66/10—Particular design of joint configurations particular design of the joint cross-sections
- B29C66/11—Joint cross-sections comprising a single joint-segment, i.e. one of the parts to be joined comprising a single joint-segment in the joint cross-section
- B29C66/112—Single lapped joints
- B29C66/1122—Single lap to lap joints, i.e. overlap joints
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
- B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
- B29C66/45—Joining of substantially the whole surface of the articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
- B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
- C08J5/122—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using low molecular chemically inert solvents, swelling or softening agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/16—Ethene-propene or ethene-propene-diene copolymers
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Lining Or Joining Of Plastics Or The Like (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE:
A process for the solution welding of molded or shaped polymeric articles formed of solution-weldable syn-thetic resin, to one another, which comprises applying a solution welding agent to one or both of the synthetic resin surfaces to be bonded together, the agent containing an organic solvent mixture or an organic solvent mixture contai-ning synthetic resin dissolved therein, and then pressing the surfaces to be bonded against each other. The molded synthetic resin articles is formed of an ethylene-propylene-diene terpolymer and/or ethylene-propylene copolymer contai-ning conventional additives for the resin, and the solvent mixture containing 20-60% by volume of an aromatic solvent and 80-40% by volume of an alipahtic solvent with a boiling range of 60-160°C.
A process for the solution welding of molded or shaped polymeric articles formed of solution-weldable syn-thetic resin, to one another, which comprises applying a solution welding agent to one or both of the synthetic resin surfaces to be bonded together, the agent containing an organic solvent mixture or an organic solvent mixture contai-ning synthetic resin dissolved therein, and then pressing the surfaces to be bonded against each other. The molded synthetic resin articles is formed of an ethylene-propylene-diene terpolymer and/or ethylene-propylene copolymer contai-ning conventional additives for the resin, and the solvent mixture containing 20-60% by volume of an aromatic solvent and 80-40% by volume of an alipahtic solvent with a boiling range of 60-160°C.
Description
35~
The present invention relates to a solution wel-ding agent or medium for bonding; i.e., welding together molded articles or components, especially flat articles, such as sealing sheets of synthetic resins, which agent contains a solvent mixture or a solvent mixture with dissolved synthetic resin, respectively.
The present invention also relates to a process for solution welding of molded articles, especially flat shapes such as sealing sheets Eor the construction industry made of solution-weldable synthetic resins.
Solution welding is a type of bonding for two components, especially based on the same material, wherein the mutually facing surfaces to be bonded together are softened by means of a readily volatile solvent and pressed against each other. After volatilization of the solvent, a homogeneous bond is obtained without an intermediate layer of a heterogeneous material. Solution welding can be uti-lized in a large sector of thermoplastic synthetic resins;
in this connection, reference is had, for example, to the known solution welding of sealing sheets of plasticized PVC
or polyisobutylene, described, for instance, in the book Bauen mit Kunststoffen (Building with Synthetic Resins) by Hansjurgen Saechtling, Carl Hanser Publishers, Munich tl973), pages 127, 235 and 237, etc. A specific solution welding agent containing a solvent and/or a solvent mixture as well as synthetic resin additives, especially for polyisobutylene sheets, is described, for example, in DAS (German Published Application) 2,506,881.
The conventional solution welding agents, for example, on the basis of tetrahydrofuran for plasticized PVC, or petroleum spirits or carbon tetrachloride or cyclo-- 1 - .~, . . ~
: ! J
~Z~3~
hexanone for polyisobutylene are, however, incapable of solution welding, with sufficient homogeneousness, molded articles on the basis of elastomeric synthetic resins, especially on the basis of ethylene-propylene-diene terpo-lymers or ethylene-propylene copolymers. The invention is based on the object of discovering a suitable solution welding agent and a process technique to homogeneously bond together molded articles on the basis of elastomeric synthetic resins, likewise utilizing the solution welding method.
According to the present invention there is pro-vided a process for the solution welding of molded or shaped polymeric articles formed of solution-weldable synthetic resin, to one another, which comprises applying a solution welding agent to one or both of the synthetic resin surfaces to be bonded together, said agent containing an organic solvent mixture or an organic solvent mixture containing synthetic resin dissolved therein, and then pressing the surfaces to be bonded against each other; the molded synthetic resin articles being formed of an ethylene-propylene~diene terpolymer and/or ethylene-propylene copolymer co~taining conventional additives for said resin, and said solvent mixture containing 20-60% by volume of an aromatic solvent and 80-40% by volume of an alipahtic solvent with a boiling range of 60-160C-Preferably, in the process the solution weldingagent may contain 75-90% by weight of the solvent mixture and, dissolved therein, 25-10% by weight of elastomeric syn-thetic resin on the basis of EPDM and/or EPM dissolved therein.
Preferably, the solvent mixture may contain 20-30%
by volume of toluene and 80-70% by volume of petroleum spirits with a boiling range from 95 to 160C for solution-welding the molded synthetic resin articles at temperaturefrom 15 and thereabove.
Preferably, the solvent mixture may contain 40-60%
by volume of toluene and 60-40% by volume of petroleum spirits with a boiling range from 60 to 95C for solution-welding the molded synthetic resln articles at temperatures from 5C and thereabove.
The resin articles are preferably devoid of vulca-nization accelerator and contain additives.
The additives may comprise: fillers which may comprises carbon black, silicic acid anhydride and silica, extenders, stabilizers, antiaging compounds, mold release agents, processing aids, or pigments.
According th the present invention there is also provided process for the solution welding of molded or shaped polymeric articles formed of a synthetic resin comprising an ethylene-propylene-diene terpolymer and/or ethylene-propylene copolymer that is devoid of vulcanization accele-rator and contains conventional additives for said resin, to one another, which comprises applying a solution welding agent to one or both of the synthetic resin surfaces to be bonded together, said agent containing an organic solvent mixture or an organic solvent mixture containing said synthetic resin dissolved thereln, and then pressing the surfaces to be bonded against each other; said solvent mixture containing 20-50% by volume of an aromatic solvent and 80-40~ by volume of an aliphatic solvent with a boiling range of 60-160C
and the applying of the solution welding agent and the pressing of the surfaces against each other being effected at tempera-ratures starting at 5C and thereabove.
.
~22~ 6 Accord.ing to the present lnvention also provided a process for the solut.ion welding of molded or shaped poly-meric articles formed of a synthetic resin comprising an ethylene-propylene-diene terpolymer and/or ethylene-propylene copolymer that is devoid of vulcani.zation accelerator and contains conventional additives for said resin, to one another, which comprises applying a solution welding agent to one or both of the synthetic resin surfaces to be bonded together, said agent containing an organic solvent mixture or an organic solvent mixture containing said synthetic resin dissolved therein, and then pressing the surfaces to be bonded against each other; said solvent mixture containing 20-60% by volume of an aromatic solvent selected from the group consisting of xylene and toluene and 80-40% by volume of an aliphatic solvent comprises petroleum spirits containing 5 to 12 atoms with a boiling range of 60-160C and the applying of the solution welding agent and the pressing of the surfaces against each other being effected at temperatures starting at 5C and thereabove.
In the present invention, there is used a solution welding agent for welding together molded or shaped polymeric articles of synthetic elastomeric resins, on the basis of ethylene-propylene-diene terpolymers and/or ethylene-propylene copolymers, which comprises an organic solvent mixture con-taining 20-60% by volume of an aromatic solvent and 80 40%
by volume of an aliphatic solvent with a boiling rang from 60 to 160C.
Preferably, the solution welding agent contains customary additives.
It is possible by means of the solution welding agent proposed in this invention to apply the 3~6 solution welding method even in case of the specific elasto-meric synthetic resins recited above, and to obtain homo-geneous, tight bonds with adequate dissolving effect (surface dissolution) after evaporation of the solvent.
The essential aspect of the invention is the use of a solvent mixture with an aliphatic proportion (or compo-nent) and an aromatic proportion.
Toluene (methylbenzene) is preferably employed as the aromatic proportion. Xylene is likewise possible as the aromatic solvent, but toluene proves to be more effectlve.
~ suitable aliphatic solvent is, in particular, petroleum spirits on the basis of a mixture of saturated aliphatic hydrocarbons containing 5-12 carbon atoms. The petroleum spirits can also contain additionally unsaturated naphthenic and aromatic hydrocarbons is small amounts; e.g., 1 to 5% by weight. An essential advantage of the solution welding agent proposed in accordance with the invention is its inexpensive manufacture.
Depending on the application range for processing, varying compositions of the solvent mixture are provided according to the invention. When solution welding is effected at temperatures starting with 15C and above, a solution welding agent is preferably utilized consisting essentially of a solvent mixture containing 20-30% by volume of toluene and 80-70% by volume of petroleum spirits with a boiling range of 95-160C. ~owever, if circumstances make it neces-sary to conduct the solution welding step at even lower tem-peratures, then a solution welding agent is suggested in accordance with this invention consisting essentially of a solvent mixture containing 40-60% by volume of toluene and ,~ , 60-40% by volume of petroleum spirits with a boiling range of 60-95C. With this agent, the process can be carried out at a temperature as low as 5C and above. It may be advanta-geous for certain bonding areas of molded synthetic resin articles, for example also the filling of joints or the use of smaller amounts of solvent, to add to the solvent mixture a dissolved synthetic resin.
A preferred composition of such a solution welding agent provides the use of 75-90% by weight of solvent mixture and 25-10% by weight of elastomeric synthetic resin on the basis of EPDM and/or EPM dissolved therein, optionally with conventional additives for these elastomers. In this case, the solvent mixture can be combined either with merely the elastomeric synthetic resin or also a synthetic resin molding composition additionally containing additives, such as sta-bilizers, mold release agents, extenders, pigments, carbon black. However, it is more pratical not to add fillers, such as chalk, talc, silica, etc., as additives to the solu-tion welding agent, since this addition could reduce the strength of the welding bond.
Generally, the sheet comprises from 40 to 58%
by weight of the fillers; whereas the other additives may 25 vary from 7 to 18% by weight and 35 to 46 by weight of elasto-meric resin.
The sealing sheet material, used in the present invention, combines advantageously the benefits of the elastomeric, vulcanizable but not completely vulcanized synthetic resinsl especially regarding weathering stability, with the benefits provided by the thermoplastic synthetic resins; namely, weldability, especially solution weldability, attained by means of the solution welding agent proposed by the present invention.
The multiple-layer sealing sheet material can be manufactured, for example, by calendering of sheets, espe-cially in thicknesses of 0.6 to 0.9 mm, in accordance withthe individual layers, and rolling or laminating these sheets together with the use of heat and pressure, with the embed-ding of the reinforcing insert therein. It is economical, in this connection, to employ the same sheeting for each of the outer layers.
In a advantageous composition of the sealing sheet, the synthetic resin layers may contain the following:
35-46% by weight of EPDM or EPM or mixture of EPDM or EPM
40-58% by weight of fillers, of these up to 50 by weight of carbon black 5-12% by weight of extenders 10- 0.1% by weight of stabilizers and antiaging coupounds 5- 1.9% by weight of mold release agents and auxiliary processing media.
Preferably, the layers contain as fillers:
19-22% by weight of carbon black, reinfcrcing or semi-reinforcing types 26-31% by weight of silicic acid anhydride or of silica (silicic acid anhydride and kaolinite with a particle size smaller than 20 ~m and at least 40% proportion of smaller than 2 ~m3, based on 100% by weight of layer, for an economical manufac-ture of the sealing sheet, for improving the strength, and as a processing aid. This composition provides good processa-bility, especially, suitability for calendering.
The elastomeric synthetic resins selected are in particular, partially crys-talline ethylene-propylene-diene terpolymers (EPDM) or partially crystalline ethylene-pro-pylene copolymers (EPM) and/or mixtures thereof in order to ensure the high demands to be met by a sealing sheet with respect to mechanical properties, low-temperature stability, perforation strength even at higher temperatures, low shrinkage, tear strength, extensibility, and dimensional stability. An EPM is preferred with an ethylene content of 65% by weight or larger and a propylene content of 35% by weight or smaller and an EPDM is preferred with an ethylene content of at least 65% by weight, a propylene content of not more than 30% by weight and maximally up to 8% by weight of a diene component, preferably less than 5~ by weight of a diene component. A
suitable diene component is, for example, ethylidene norbornene hexadiene or cyclopentadiene. The minimum degree of partial crystallinity of the EPDM or EPM employed is determined according to the DSC method in a differential scanning calori-meter measuring the melting curve. The maximum of the melting peak, measured at temperature TS in C according to the DSC
curve is designated as an endothermal peak which can be verynarrowly defined, but can also encompass a range. With ethylene-propylene terpolymers, the temperature TS is in the range around 50C. The amount of heat required for melting, the so-called melting heat ~Hs, likewise measured according to the DSC method, then yields information on the presence of crystalline blocks in the ethylene-propylene-diene ter-polymer or ethylene-propylene copolymer. Those partially crystalline EPDM or EPM elastomers with a melting heat of at least 10 J/g are preferably employed.
For selecting suitable elastomeric synthetic resins, especially EPDM and EPM, the strength thereof is likewise of importance, those EPDM and EPM being utilized which exhibit a tear strength of at least 5 N/mm measured according to 3~
DIN 53 455 (~erman Industrial Standard).
The high parting strength of at least 100 N/5 cm of the multiplelayer sealing sheet is attained especially by choosing suitable reinforcing inserts with correspondingly large air interspaces between the warp and weft threads, making i~ possible for the synthetic resin layers to extend therethrough to an adequate degree and thereby to form a substantially homogeneous bond. In this connection, glass fabrics are preferably employed, imparting to the multiple-layer sealing sheet a high dimensional stability and diminish-ing the shrinkage, much feared in the building industry, under alternating temperature stresses during the course of summer/winter weathering.
~ ikewise of decisive importance is the selection of suitable fillers for the synthetic resin layers and additives which cooperate synergistically and which improve the properties of the sealing sheet, especially its mechanical characteristics. In this connection, an essential component is constituted by semiactive or active carbon blacks, so-called reinforcing blacks, wherein the layers contain between 19 and 25~ by weight, preferably 19-22% by weight of carbon blacks. For example, suitable are carbon blacks produced according to the furnace method exhibiting average particle sizes of between 30 and 60 nm and a BET surface of between 30 and 60. Especially the carbon black improves the strenght of the sheet and improves the processability.
As reinforcing filler and simultaneously for making the product less expensive, silicic acid anhydride or silica is preferably employed; i.e., silica is a mixture of silicic acid anhydride and kaolinite, wherein the particle sizes should be smaller than 20 ~m, and of these at least 40%
- 8a -~2Z~
should be smaller than 2 ~m. ~owever, it is also possible to replace up to 2/3 of the silica proportion by other selected fillers, likewise in a very fine-grained form, such as chalk, kaolin, talc, baryte, silicic acid anhydride and/or glass fibers, or mix-tures thereof.
Additionally, the layers of the sealing sheet con-tain stabilizers and antiaging agents, especially on the basis of sterically hindered phenolic antioxidants, phenolic phosphites, thioesters of aliphatic carboxylic acids, and similar materials.
Especially suitable as mold release agents for processing are metallic soaps, for example, calcium soaps, calcium stearate, zinc stearate, and as auxiliary processing agents especially montanic acid esters and/or hydrogeneted hydro-carbon resins. Moreover, for processing EPDM and EPM, the use of extender oils on an aliphatic and/or naphthenic basis is required. A preferred structure for the synthetic resin layers according to the invention provides that they contain 35-46% by weight of EPDM and/or EPM, 31-26% by weight of fillers, such as chalk, kaolin, talc, baryte, silicic acid anhydride and/or glass fibers in mixtures with silica or solely silica, 12-7% by weight of aliphatic and/or naphthenic extender oils, 1.0 - 0.1% by weight of stabilizers and antiaging agents on the basis of sterically hindered phenolic antioxidants, phenolic phosphites, thioesters of aliphatic carboxylic acids or the like, 25-19% by weight of reinforcing carbon blacks, 5.0 - 0.1% by weight of mold release agents on the basis of metallic soaps, 2.3 - 1.8% by weight of processing aids, such as montanic acid esters, hydrogenated hydrocarbon resins. Additionally t the sealing sheet can be provided with other customary additives, such as pigments for coloring and other materials.
The properties of the sealing sheet of this invention are excellently adapted to all demands to be met in the building industry. Besides showing high performance _ g 3~
at room temperature, the sealing sheet performs at low temperatures of down to -60 C as well as at high temperatures up to about 100C. Weathering stability and biological resistance are likewise present.
It is, moreover, an objective of the invention to provide a sealing sheet on the basis of elastomeric synthetic resins which can be bonded also by means of the well-proven solution welding or room-temperature welding (cold welding) method. The sealing sheet can be solution-welded advan-tageously by means of a solution welding agent on the basis of a mixture of toluene and petroleum spirits, it being possible to produce seam bonds of flawless quality starting with temperatures as low as above 0C, especially above 5C, in the open air at the building site~
The following examples serve for explaining the invention without limiting same.
EXAMP~E 1 For obtaining the multiple-layer sealing sheet material according to the sole figure in the accompanying drawing, sheets having a thickness of 0.75 mm made up of a material composition A according to Table 1, are utilized for the outer layers 1, 3; and a glass fabric with a weight per unit area of 30 g/m2 with a nonslip finish on the basis of vinyl propionate dispersion is used for the reinforcing insert 2; these layers are combined into the multiple layer sealing sheet by calendering.
_ _ _ __ Composition A Parts by Weight _ .
EPDM with 67% by weight ethylene 27% by weight propylene 6% by weight ethylidene 40.0 norbornene s 14 J/g, 2 Tear strength 11.2 N/mm _ _ ~ - ~ ~
Sillitin*(Silica) 27.0 I _ i .
Extender oil 8.0 Hydrocarbon resin 2.0 _ .
Carbon black, semiactive 22.5 Calcium soap 0.3 Antioxidants 0.2 The thus-produced multiple-layer sealing sheet has the following properties:
Thickness DIN 53370 1.5 mm Tear strength DIN 53354 longitudinal/
transverse, fabric ~400/ >400 N/5 cm * Sillitin is a Trade mark 3~
Tear strength DIN 53354 longitudinal/transverse, sheet >450/ >450 N/5 cm Elongation at rupture DIN 53354 long.itudinal/transverse, fabric
The present invention relates to a solution wel-ding agent or medium for bonding; i.e., welding together molded articles or components, especially flat articles, such as sealing sheets of synthetic resins, which agent contains a solvent mixture or a solvent mixture with dissolved synthetic resin, respectively.
The present invention also relates to a process for solution welding of molded articles, especially flat shapes such as sealing sheets Eor the construction industry made of solution-weldable synthetic resins.
Solution welding is a type of bonding for two components, especially based on the same material, wherein the mutually facing surfaces to be bonded together are softened by means of a readily volatile solvent and pressed against each other. After volatilization of the solvent, a homogeneous bond is obtained without an intermediate layer of a heterogeneous material. Solution welding can be uti-lized in a large sector of thermoplastic synthetic resins;
in this connection, reference is had, for example, to the known solution welding of sealing sheets of plasticized PVC
or polyisobutylene, described, for instance, in the book Bauen mit Kunststoffen (Building with Synthetic Resins) by Hansjurgen Saechtling, Carl Hanser Publishers, Munich tl973), pages 127, 235 and 237, etc. A specific solution welding agent containing a solvent and/or a solvent mixture as well as synthetic resin additives, especially for polyisobutylene sheets, is described, for example, in DAS (German Published Application) 2,506,881.
The conventional solution welding agents, for example, on the basis of tetrahydrofuran for plasticized PVC, or petroleum spirits or carbon tetrachloride or cyclo-- 1 - .~, . . ~
: ! J
~Z~3~
hexanone for polyisobutylene are, however, incapable of solution welding, with sufficient homogeneousness, molded articles on the basis of elastomeric synthetic resins, especially on the basis of ethylene-propylene-diene terpo-lymers or ethylene-propylene copolymers. The invention is based on the object of discovering a suitable solution welding agent and a process technique to homogeneously bond together molded articles on the basis of elastomeric synthetic resins, likewise utilizing the solution welding method.
According to the present invention there is pro-vided a process for the solution welding of molded or shaped polymeric articles formed of solution-weldable synthetic resin, to one another, which comprises applying a solution welding agent to one or both of the synthetic resin surfaces to be bonded together, said agent containing an organic solvent mixture or an organic solvent mixture containing synthetic resin dissolved therein, and then pressing the surfaces to be bonded against each other; the molded synthetic resin articles being formed of an ethylene-propylene~diene terpolymer and/or ethylene-propylene copolymer co~taining conventional additives for said resin, and said solvent mixture containing 20-60% by volume of an aromatic solvent and 80-40% by volume of an alipahtic solvent with a boiling range of 60-160C-Preferably, in the process the solution weldingagent may contain 75-90% by weight of the solvent mixture and, dissolved therein, 25-10% by weight of elastomeric syn-thetic resin on the basis of EPDM and/or EPM dissolved therein.
Preferably, the solvent mixture may contain 20-30%
by volume of toluene and 80-70% by volume of petroleum spirits with a boiling range from 95 to 160C for solution-welding the molded synthetic resin articles at temperaturefrom 15 and thereabove.
Preferably, the solvent mixture may contain 40-60%
by volume of toluene and 60-40% by volume of petroleum spirits with a boiling range from 60 to 95C for solution-welding the molded synthetic resln articles at temperatures from 5C and thereabove.
The resin articles are preferably devoid of vulca-nization accelerator and contain additives.
The additives may comprise: fillers which may comprises carbon black, silicic acid anhydride and silica, extenders, stabilizers, antiaging compounds, mold release agents, processing aids, or pigments.
According th the present invention there is also provided process for the solution welding of molded or shaped polymeric articles formed of a synthetic resin comprising an ethylene-propylene-diene terpolymer and/or ethylene-propylene copolymer that is devoid of vulcanization accele-rator and contains conventional additives for said resin, to one another, which comprises applying a solution welding agent to one or both of the synthetic resin surfaces to be bonded together, said agent containing an organic solvent mixture or an organic solvent mixture containing said synthetic resin dissolved thereln, and then pressing the surfaces to be bonded against each other; said solvent mixture containing 20-50% by volume of an aromatic solvent and 80-40~ by volume of an aliphatic solvent with a boiling range of 60-160C
and the applying of the solution welding agent and the pressing of the surfaces against each other being effected at tempera-ratures starting at 5C and thereabove.
.
~22~ 6 Accord.ing to the present lnvention also provided a process for the solut.ion welding of molded or shaped poly-meric articles formed of a synthetic resin comprising an ethylene-propylene-diene terpolymer and/or ethylene-propylene copolymer that is devoid of vulcani.zation accelerator and contains conventional additives for said resin, to one another, which comprises applying a solution welding agent to one or both of the synthetic resin surfaces to be bonded together, said agent containing an organic solvent mixture or an organic solvent mixture containing said synthetic resin dissolved therein, and then pressing the surfaces to be bonded against each other; said solvent mixture containing 20-60% by volume of an aromatic solvent selected from the group consisting of xylene and toluene and 80-40% by volume of an aliphatic solvent comprises petroleum spirits containing 5 to 12 atoms with a boiling range of 60-160C and the applying of the solution welding agent and the pressing of the surfaces against each other being effected at temperatures starting at 5C and thereabove.
In the present invention, there is used a solution welding agent for welding together molded or shaped polymeric articles of synthetic elastomeric resins, on the basis of ethylene-propylene-diene terpolymers and/or ethylene-propylene copolymers, which comprises an organic solvent mixture con-taining 20-60% by volume of an aromatic solvent and 80 40%
by volume of an aliphatic solvent with a boiling rang from 60 to 160C.
Preferably, the solution welding agent contains customary additives.
It is possible by means of the solution welding agent proposed in this invention to apply the 3~6 solution welding method even in case of the specific elasto-meric synthetic resins recited above, and to obtain homo-geneous, tight bonds with adequate dissolving effect (surface dissolution) after evaporation of the solvent.
The essential aspect of the invention is the use of a solvent mixture with an aliphatic proportion (or compo-nent) and an aromatic proportion.
Toluene (methylbenzene) is preferably employed as the aromatic proportion. Xylene is likewise possible as the aromatic solvent, but toluene proves to be more effectlve.
~ suitable aliphatic solvent is, in particular, petroleum spirits on the basis of a mixture of saturated aliphatic hydrocarbons containing 5-12 carbon atoms. The petroleum spirits can also contain additionally unsaturated naphthenic and aromatic hydrocarbons is small amounts; e.g., 1 to 5% by weight. An essential advantage of the solution welding agent proposed in accordance with the invention is its inexpensive manufacture.
Depending on the application range for processing, varying compositions of the solvent mixture are provided according to the invention. When solution welding is effected at temperatures starting with 15C and above, a solution welding agent is preferably utilized consisting essentially of a solvent mixture containing 20-30% by volume of toluene and 80-70% by volume of petroleum spirits with a boiling range of 95-160C. ~owever, if circumstances make it neces-sary to conduct the solution welding step at even lower tem-peratures, then a solution welding agent is suggested in accordance with this invention consisting essentially of a solvent mixture containing 40-60% by volume of toluene and ,~ , 60-40% by volume of petroleum spirits with a boiling range of 60-95C. With this agent, the process can be carried out at a temperature as low as 5C and above. It may be advanta-geous for certain bonding areas of molded synthetic resin articles, for example also the filling of joints or the use of smaller amounts of solvent, to add to the solvent mixture a dissolved synthetic resin.
A preferred composition of such a solution welding agent provides the use of 75-90% by weight of solvent mixture and 25-10% by weight of elastomeric synthetic resin on the basis of EPDM and/or EPM dissolved therein, optionally with conventional additives for these elastomers. In this case, the solvent mixture can be combined either with merely the elastomeric synthetic resin or also a synthetic resin molding composition additionally containing additives, such as sta-bilizers, mold release agents, extenders, pigments, carbon black. However, it is more pratical not to add fillers, such as chalk, talc, silica, etc., as additives to the solu-tion welding agent, since this addition could reduce the strength of the welding bond.
Generally, the sheet comprises from 40 to 58%
by weight of the fillers; whereas the other additives may 25 vary from 7 to 18% by weight and 35 to 46 by weight of elasto-meric resin.
The sealing sheet material, used in the present invention, combines advantageously the benefits of the elastomeric, vulcanizable but not completely vulcanized synthetic resinsl especially regarding weathering stability, with the benefits provided by the thermoplastic synthetic resins; namely, weldability, especially solution weldability, attained by means of the solution welding agent proposed by the present invention.
The multiple-layer sealing sheet material can be manufactured, for example, by calendering of sheets, espe-cially in thicknesses of 0.6 to 0.9 mm, in accordance withthe individual layers, and rolling or laminating these sheets together with the use of heat and pressure, with the embed-ding of the reinforcing insert therein. It is economical, in this connection, to employ the same sheeting for each of the outer layers.
In a advantageous composition of the sealing sheet, the synthetic resin layers may contain the following:
35-46% by weight of EPDM or EPM or mixture of EPDM or EPM
40-58% by weight of fillers, of these up to 50 by weight of carbon black 5-12% by weight of extenders 10- 0.1% by weight of stabilizers and antiaging coupounds 5- 1.9% by weight of mold release agents and auxiliary processing media.
Preferably, the layers contain as fillers:
19-22% by weight of carbon black, reinfcrcing or semi-reinforcing types 26-31% by weight of silicic acid anhydride or of silica (silicic acid anhydride and kaolinite with a particle size smaller than 20 ~m and at least 40% proportion of smaller than 2 ~m3, based on 100% by weight of layer, for an economical manufac-ture of the sealing sheet, for improving the strength, and as a processing aid. This composition provides good processa-bility, especially, suitability for calendering.
The elastomeric synthetic resins selected are in particular, partially crys-talline ethylene-propylene-diene terpolymers (EPDM) or partially crystalline ethylene-pro-pylene copolymers (EPM) and/or mixtures thereof in order to ensure the high demands to be met by a sealing sheet with respect to mechanical properties, low-temperature stability, perforation strength even at higher temperatures, low shrinkage, tear strength, extensibility, and dimensional stability. An EPM is preferred with an ethylene content of 65% by weight or larger and a propylene content of 35% by weight or smaller and an EPDM is preferred with an ethylene content of at least 65% by weight, a propylene content of not more than 30% by weight and maximally up to 8% by weight of a diene component, preferably less than 5~ by weight of a diene component. A
suitable diene component is, for example, ethylidene norbornene hexadiene or cyclopentadiene. The minimum degree of partial crystallinity of the EPDM or EPM employed is determined according to the DSC method in a differential scanning calori-meter measuring the melting curve. The maximum of the melting peak, measured at temperature TS in C according to the DSC
curve is designated as an endothermal peak which can be verynarrowly defined, but can also encompass a range. With ethylene-propylene terpolymers, the temperature TS is in the range around 50C. The amount of heat required for melting, the so-called melting heat ~Hs, likewise measured according to the DSC method, then yields information on the presence of crystalline blocks in the ethylene-propylene-diene ter-polymer or ethylene-propylene copolymer. Those partially crystalline EPDM or EPM elastomers with a melting heat of at least 10 J/g are preferably employed.
For selecting suitable elastomeric synthetic resins, especially EPDM and EPM, the strength thereof is likewise of importance, those EPDM and EPM being utilized which exhibit a tear strength of at least 5 N/mm measured according to 3~
DIN 53 455 (~erman Industrial Standard).
The high parting strength of at least 100 N/5 cm of the multiplelayer sealing sheet is attained especially by choosing suitable reinforcing inserts with correspondingly large air interspaces between the warp and weft threads, making i~ possible for the synthetic resin layers to extend therethrough to an adequate degree and thereby to form a substantially homogeneous bond. In this connection, glass fabrics are preferably employed, imparting to the multiple-layer sealing sheet a high dimensional stability and diminish-ing the shrinkage, much feared in the building industry, under alternating temperature stresses during the course of summer/winter weathering.
~ ikewise of decisive importance is the selection of suitable fillers for the synthetic resin layers and additives which cooperate synergistically and which improve the properties of the sealing sheet, especially its mechanical characteristics. In this connection, an essential component is constituted by semiactive or active carbon blacks, so-called reinforcing blacks, wherein the layers contain between 19 and 25~ by weight, preferably 19-22% by weight of carbon blacks. For example, suitable are carbon blacks produced according to the furnace method exhibiting average particle sizes of between 30 and 60 nm and a BET surface of between 30 and 60. Especially the carbon black improves the strenght of the sheet and improves the processability.
As reinforcing filler and simultaneously for making the product less expensive, silicic acid anhydride or silica is preferably employed; i.e., silica is a mixture of silicic acid anhydride and kaolinite, wherein the particle sizes should be smaller than 20 ~m, and of these at least 40%
- 8a -~2Z~
should be smaller than 2 ~m. ~owever, it is also possible to replace up to 2/3 of the silica proportion by other selected fillers, likewise in a very fine-grained form, such as chalk, kaolin, talc, baryte, silicic acid anhydride and/or glass fibers, or mix-tures thereof.
Additionally, the layers of the sealing sheet con-tain stabilizers and antiaging agents, especially on the basis of sterically hindered phenolic antioxidants, phenolic phosphites, thioesters of aliphatic carboxylic acids, and similar materials.
Especially suitable as mold release agents for processing are metallic soaps, for example, calcium soaps, calcium stearate, zinc stearate, and as auxiliary processing agents especially montanic acid esters and/or hydrogeneted hydro-carbon resins. Moreover, for processing EPDM and EPM, the use of extender oils on an aliphatic and/or naphthenic basis is required. A preferred structure for the synthetic resin layers according to the invention provides that they contain 35-46% by weight of EPDM and/or EPM, 31-26% by weight of fillers, such as chalk, kaolin, talc, baryte, silicic acid anhydride and/or glass fibers in mixtures with silica or solely silica, 12-7% by weight of aliphatic and/or naphthenic extender oils, 1.0 - 0.1% by weight of stabilizers and antiaging agents on the basis of sterically hindered phenolic antioxidants, phenolic phosphites, thioesters of aliphatic carboxylic acids or the like, 25-19% by weight of reinforcing carbon blacks, 5.0 - 0.1% by weight of mold release agents on the basis of metallic soaps, 2.3 - 1.8% by weight of processing aids, such as montanic acid esters, hydrogenated hydrocarbon resins. Additionally t the sealing sheet can be provided with other customary additives, such as pigments for coloring and other materials.
The properties of the sealing sheet of this invention are excellently adapted to all demands to be met in the building industry. Besides showing high performance _ g 3~
at room temperature, the sealing sheet performs at low temperatures of down to -60 C as well as at high temperatures up to about 100C. Weathering stability and biological resistance are likewise present.
It is, moreover, an objective of the invention to provide a sealing sheet on the basis of elastomeric synthetic resins which can be bonded also by means of the well-proven solution welding or room-temperature welding (cold welding) method. The sealing sheet can be solution-welded advan-tageously by means of a solution welding agent on the basis of a mixture of toluene and petroleum spirits, it being possible to produce seam bonds of flawless quality starting with temperatures as low as above 0C, especially above 5C, in the open air at the building site~
The following examples serve for explaining the invention without limiting same.
EXAMP~E 1 For obtaining the multiple-layer sealing sheet material according to the sole figure in the accompanying drawing, sheets having a thickness of 0.75 mm made up of a material composition A according to Table 1, are utilized for the outer layers 1, 3; and a glass fabric with a weight per unit area of 30 g/m2 with a nonslip finish on the basis of vinyl propionate dispersion is used for the reinforcing insert 2; these layers are combined into the multiple layer sealing sheet by calendering.
_ _ _ __ Composition A Parts by Weight _ .
EPDM with 67% by weight ethylene 27% by weight propylene 6% by weight ethylidene 40.0 norbornene s 14 J/g, 2 Tear strength 11.2 N/mm _ _ ~ - ~ ~
Sillitin*(Silica) 27.0 I _ i .
Extender oil 8.0 Hydrocarbon resin 2.0 _ .
Carbon black, semiactive 22.5 Calcium soap 0.3 Antioxidants 0.2 The thus-produced multiple-layer sealing sheet has the following properties:
Thickness DIN 53370 1.5 mm Tear strength DIN 53354 longitudinal/
transverse, fabric ~400/ >400 N/5 cm * Sillitin is a Trade mark 3~
Tear strength DIN 53354 longitudinal/transverse, sheet >450/ >450 N/5 cm Elongation at rupture DIN 53354 long.itudinal/transverse, fabric
2/2%
Elongation at rupture DIN 53354 longitudinal/transverse, sheet >450/ >450~
Specific gravity DIN 53479 1270 kg/m3 Parting strength of layers DIN 53357 ~100 N/5 cm Dimensional change at + ~0C, 6 hour period DIN 53377 <0.5%
Cold impact strength VDCH 22-02 218 K
To weld the sealing sheets together with one another, the solution welding agent employed is, for example, a mixture of 1 part by volume of toluene and 3 parts by volume of petroleum spirits with a boiling range from 100 to 140C. The sealing sheet is welded in this case at temperatures starting from 15C on upward by coating the overlapping seams of the sheets to be welded in a width of about 5 to 8 cm with a brush or the like with the solution welding agent and continously directly after the coating the seams are pressed together with a pressure of about 0,01 to 0~1 N/cm2 during a time of about 10 to 30 sec. by means of a sandbag or pressure roll.
If the above-described sealing sheets are to be welded together at even lower temperatures, the step can be performed, for example, with a solution welding agent made up of 1 part by volume of toluene and 1 part by volume of petroleum spirits with a boiling range from 60 to 95C, in which case the operation can be performed even starting at temperatures of 5C on upward in the outside air, and adequate venting and evaporation of the solvents is possible - ~.2 -to establish a flawless homogeneous bond by means of solution welding. In case the temperature during installation i~
very low, 5C or less, it is possible to warm up the sheets by hot air before or after applying the solution welding agent to accelerate the welding.
For the solution welding of joints and optionally for the securing of seam junctions, or the like, it is also possible to employ a solution welding agent which contains a synthetic resin dissolved therein. For the sealing sheet of the composition set forth in Table 1, for example, a so-lution welding agent, called "liquid film," having the follow-ing composition is utilized for securing of joints:
84% by weight of solvent mixture made up ot
Elongation at rupture DIN 53354 longitudinal/transverse, sheet >450/ >450~
Specific gravity DIN 53479 1270 kg/m3 Parting strength of layers DIN 53357 ~100 N/5 cm Dimensional change at + ~0C, 6 hour period DIN 53377 <0.5%
Cold impact strength VDCH 22-02 218 K
To weld the sealing sheets together with one another, the solution welding agent employed is, for example, a mixture of 1 part by volume of toluene and 3 parts by volume of petroleum spirits with a boiling range from 100 to 140C. The sealing sheet is welded in this case at temperatures starting from 15C on upward by coating the overlapping seams of the sheets to be welded in a width of about 5 to 8 cm with a brush or the like with the solution welding agent and continously directly after the coating the seams are pressed together with a pressure of about 0,01 to 0~1 N/cm2 during a time of about 10 to 30 sec. by means of a sandbag or pressure roll.
If the above-described sealing sheets are to be welded together at even lower temperatures, the step can be performed, for example, with a solution welding agent made up of 1 part by volume of toluene and 1 part by volume of petroleum spirits with a boiling range from 60 to 95C, in which case the operation can be performed even starting at temperatures of 5C on upward in the outside air, and adequate venting and evaporation of the solvents is possible - ~.2 -to establish a flawless homogeneous bond by means of solution welding. In case the temperature during installation i~
very low, 5C or less, it is possible to warm up the sheets by hot air before or after applying the solution welding agent to accelerate the welding.
For the solution welding of joints and optionally for the securing of seam junctions, or the like, it is also possible to employ a solution welding agent which contains a synthetic resin dissolved therein. For the sealing sheet of the composition set forth in Table 1, for example, a so-lution welding agent, called "liquid film," having the follow-ing composition is utilized for securing of joints:
84% by weight of solvent mixture made up ot
3 parts by volume of petroleum spirits, boiling point 100-160C, and 1 part by volume of toluene 16% by weight of a synthetic resin composition of 40 parts by weight of EPDM (according to Table l);
8 parts by weight of extender oil;
2 parts by weight of hydrocarbon resin;
22.5 parts by weight of semiactive carbon black;
0.3 part by weight of calcium soap; and 0.2 part by weight of antioxidants.
8 parts by weight of extender oil;
2 parts by weight of hydrocarbon resin;
22.5 parts by weight of semiactive carbon black;
0.3 part by weight of calcium soap; and 0.2 part by weight of antioxidants.
Claims (17)
1. A process for the solution welding of molded or shaped polymeric articles formed of solution-weldable synthetic resin, to one another, which comprises applying a solution welding agent to one or both of the synthetic resin surfaces to be bonded together, said agent containing an organic solvent mixture or an organic solvent mixture containing synthetic resin dissolved therein, and then pressing the surfaces to be bonded against each other; the molded synthetic resin articles being formed of an ethylene-propylene-diene terpolymer and/or ethylene-propylene copoly-mer containing conventional additives for said resin, and said solvent mixture containing 20-60% by volume of an aromatic solvent and 80-40% by volume of an alipahtic solvent with a boiling range of 60-160°C.
2. A process according to claim 1, wherein said solution welding agent contains 75-90% by weight of the solvent mixture and, dissolved therein, 25-10% by weight of elastomeric synthetic resin on the basis of EPDM and/or EPM dissolved therein.
3. A process according to claim 1, wherein said solvent mixture contains 20-30% by volume of toluene and 80-70% by volume of petroleum spirits with a boiling range from 95° to 160°C for solution-welding the molded synthetic resin articles at temperature from 15° and thereabove.
4. A process according to claim 1, wherein said solvent mixture contain 40-60% by volume of toluene and 60-40% by volume of petroleum spirits with a boiling range from 60° to 95°C for solution-welding the molded synthetic resin articles at temperatures from 5°C and thereabove.
5. A process according to claim 1, wherein said resin articles are devoid of vulcanization accelerator and contain additives.
6. A process according to claim 5, wherein said additives comprise: fillers, silicic acid anhydride and silica, extenders, stabilizers, antiaging compounds, mold release agents, processing aids, or pigments.
7. A process according to claim 6, wherein said fillers comprise carbon black.
8. A process for the solution welding of molded or shaped polymeric articles formed of a synthetic resin comprising an ethylene-propylene-diene terpolymer and/or ethylene-propylene copolymer that is devoid of vulcanization accelerator and contains conventional additives for said resin, to one another, which comprises applying a solution welding agent to one or both of the synthetic resin surfaces to be bonded together, said agent containing an organic solvent mixture or an organic solvent mixture containing said synthetic resin dissolved therein, and then pressing the surfaces to be bonded against each other; said solvent mixture containing 20-60% by volume of an aromatic solvent and 80-40% by volume of an aliphatic solvent with a boiling range of 60-160°C and the applying of the solution welding agent and the pressing of the surfaces against each other being effected at temperatures starting at 5°C and thereabove.
9. A process according to claim 8, wherein said solution welding agent contain 75-90% by weight of the solvent mixture and, dissolved therein, 25-10% by weight of the synthetic resin including said additives for said synthetic resin.
10. A process according to claim 8, wherein said resin articles contain additives.
11. A process according to claim 10, wherein said additives include fillers, carbon black, silicic acid anhydride and silica, extenders, stabilizers, antiaging compounds, mold release agents, processing aids and/or pigments.
12. A process for the solution welding of molded or shaped polymeric articles formed of a synthetic resin comprising an ethylene-propylene-diene terpolymer and/ or ethylene-propylene copolymer that is devoid of vulcanization accelerator and contains conventional additives for said resin, to one another, which comprises applying a solution welding agent to one or both of the synthetic resin surfaces to be bonded together, said agent containing an organic solvent mixture or an organic solvent mixture containing said synthetic resin dissolved therein, and then pressing the surfaces to be bonded against each other; said solvent mixture containing 20-60% by volume of an aromatic solvent selected from the group consisting of xylene and toluene and 80-40% by volume of an aliphatic solvent comprises petroleum spirits containing 5 to 12 carbon atoms with a boiling range of 60-160°C and the applying of the solution welding agent and the pressing of the surfaces against each other being effected at temperatures starting at 5°C and thereabove.
13. A process according to claim 12, wherein said solution welding agent contain 75-90% by weight of the solvent mixture and, dissolved therein, 25-10% by weight of the synthetic resin including said additives for said synthetic resin.
14. A process according to claim 12, wherein said resin articles contain additives.
15. A process according to claim 14, wherein said additives include fillers, carbon black, silicic acid anhydride and silica, extenders, stabilizers, antiaging compounds, mold release agents, processing aids and/or pigments.
16. A process according to claim 12, wherein said solution welding agent contains an organic solvent mixture wherein the aliphatic solvent comprises the petroleum distillates with a boiling point of from 60° to 160°C, said petroleum spirits containing additional unsaturated naphthenic and aromatic hydrocarbons in amounts of from 1 to 5% by weight.
17. A process according to claim 1, 8 or 12, wherein said welding agent is free of cross-linking agent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3150022.6 | 1981-12-17 | ||
| DE19813150022 DE3150022A1 (en) | 1981-12-17 | 1981-12-17 | SOURCE WELDING AGENT AND METHOD FOR SWELL WELDING PLASTIC MOLDED BODIES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1224396A true CA1224396A (en) | 1987-07-21 |
Family
ID=6148999
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000417772A Expired CA1224396A (en) | 1981-12-17 | 1982-12-15 | Solution welding material and process for solution welding of plastics shaped bodies |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0082314A1 (en) |
| JP (1) | JPS58111877A (en) |
| BR (1) | BR8207347A (en) |
| CA (1) | CA1224396A (en) |
| DE (1) | DE3150022A1 (en) |
| ES (1) | ES518265A0 (en) |
| HU (1) | HU184594B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5228938A (en) * | 1991-06-12 | 1993-07-20 | The Goodyear Tire & Rubber Company | Rubber surface treatment and products derived therefrom |
| JP2010538142A (en) * | 2007-09-05 | 2010-12-09 | エルヤ・リサイクリング・リミテッド | Adhesive formulation and multilayer assembly |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2506881B2 (en) * | 1975-02-18 | 1977-03-10 | Be Be Ge Gesellschaft für Boden-, Bauten- und Umweltschutz mbH & Co KG, 1000 Berlin | METHOD FOR SOURCE WELDING OF PLASTIC SHAPED BODIES AND / OR PLASTIC FLATS AND A SUITABLE SOURCE WELDING AGENT |
| DE3023946A1 (en) * | 1980-06-26 | 1982-01-14 | Lechler Chemie Gmbh, 7000 Stuttgart | Aromatic hydrocarbon and tert. butanol solvent mixt. - for two component epoxy! resin and polyurethane system |
-
1981
- 1981-12-17 DE DE19813150022 patent/DE3150022A1/en not_active Withdrawn
-
1982
- 1982-11-19 EP EP82110696A patent/EP0082314A1/en not_active Withdrawn
- 1982-12-15 JP JP57218507A patent/JPS58111877A/en active Pending
- 1982-12-15 CA CA000417772A patent/CA1224396A/en not_active Expired
- 1982-12-16 ES ES518265A patent/ES518265A0/en active Granted
- 1982-12-16 BR BR8207347A patent/BR8207347A/en unknown
- 1982-12-16 HU HU824072A patent/HU184594B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ES8405822A1 (en) | 1984-06-16 |
| DE3150022A1 (en) | 1983-06-30 |
| JPS58111877A (en) | 1983-07-04 |
| HU184594B (en) | 1984-09-28 |
| BR8207347A (en) | 1983-10-18 |
| EP0082314A1 (en) | 1983-06-29 |
| ES518265A0 (en) | 1984-06-16 |
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