AU599315B2 - Metal bonding adhesive - Google Patents
Metal bonding adhesive Download PDFInfo
- Publication number
- AU599315B2 AU599315B2 AU57504/86A AU5750486A AU599315B2 AU 599315 B2 AU599315 B2 AU 599315B2 AU 57504/86 A AU57504/86 A AU 57504/86A AU 5750486 A AU5750486 A AU 5750486A AU 599315 B2 AU599315 B2 AU 599315B2
- Authority
- AU
- Australia
- Prior art keywords
- metal
- bonding adhesive
- primer
- weight
- adhesive according
- 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.)
- Ceased
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
- C09J133/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Description
1111-2 114 u6vLysVnc L zAxMAnjs bdouwl1!!4 fBjapq o zkXMAr11SdONW 1rH0A9oJDV 'Id 01 I IIllI=-= 1111.25 1.
111 io6 I I I I I I I I i i I I I I I I I I I I I 'I
AUSTRALIA
Patents Act 599,3 COMPLETE SPECIFICATION
(ORIGINAL)
Class Int. Class Application Number: Lodged: Complete Specification Lodged: Accepted: Published:4 Priority Related Art: t~4 This documnrt contaiit arnmm.ilmnts mad-, Section 49 and is correct !ui printing.J APPLICANT'S REF.: Name(s) of Applicant(s): TEROSON GmabH- Case 2897 Address(es) of Applicant(s): Actual. Inventor(s): Hans-Bunte-Strasse 4, 69Q0 Heidelberg 1, West Germany Gunter Butschbacher Addlress for Service is: PHILLIPS, ORMONDE AND FTZPATRICK Patent and Trade Mark Attorneys 367 Collins Street Melbourne, Australia, 3000 Complete Specification for the invention entitled: METAL BONDING ADHESIVE The following statement is a full descriptioia of this invention, including the best method. of performing It known to applicant(s): P'10/184 The invention relates to a metal-bonding adhesive in the form of a plastisol of an acrylic resin, having heterocyclic groups with at least one N- atom in the ring, plasticizers, a primer nnd optionally inert fillers, as well as other additives.
Plastisols based on acrylate polymers are already known. German patent 24 54 235 describes an acrylate- based plastisol, which gels on heating to higher temperatures and which is storage- stable at ambient temperature, which contains a methylmethacrylatecopolymer, a copolymeros compatible organic plasticizer, optionally inert fillers, as well as a o other conventional additives, as well as optionally a primer. Suitable primers are triethylene glycol dimethacrylate, trimethylol o trimethacrylate combined with peroxides, which decompose at the gelling temperature and initiate a radical polymerization of the primer, liqui o or solid phenolic or resorcinol resins with a low formaldehyde content, 6eoo 0o° epoxy resins with heat- reacting hardeners, such as acetoguanamine or So dicyandiamide and finally aminosilanes. The thus obtained plastisols *00 0 are particularly suitable for the corrosion and abrasion protection of steel sheets, e.g. as an underbody protection for cars. However, the o 00 4O00 adhesion characteristics are not sufficiently good to enable said o 0 plastisols to also be used as metal-bonding adhesives.
It is known from German patent 25 29 732, that the adhesion characteristics of such a plastisol can be improved, in that 0.1 to 10% by weight of one or more copolymerizable monomers are polymerized into the polymer or copolymer and which contain a heterocyclic group with at least one N- atom in the ring. To further improve the adhesion, an additional crosslinking agent reacting with the heterocyclic group of the polymerizedin comonomer can be added to the plastisol. Crosslinking agents suitable umcr wnCess requircu L.-Au i LL To: The Commissioner of Patents Title Techn. Manage. Mgr. of so l and P18/7/78 PHILLIPS ORMONDE FITZPATRICK Legai Patent and Trade Mark Attorneys 367 Collins Street Melbourne, Australia STUART TAYLOR 2 for this purpose are epoxy resins and polybasic carboxeylic acids, such as benzenetricarboxeylic acid, aldipic acid, maleic acid and itac'nic acid. The plastisols obtained in this way have a much better adhesion and are suitable for the bonding of degreased or cleaned metal sheets and electrophoretically primed metal sheets.
The joining of sheet metal parts in the metal processing industry, e.g. in the car industry, is made particularly difficult in that as a result of different pretreatments, the sheets have the most varied ji surface characteristics. Thus, e.g. electrolytcally galvanized sheets, ii i'i hot-dip galvanized sheets, as well as sheets coated with deep drawing oils and/or corrosion inhibiting oils are successively used and are to be i joined together. Although the known plastisols have good adhesion Searacteristics on certain surface types, they fail on others.
The problem of the present invention is therefore to provide a metalbonding adhesive for overcoming this disadvantage which, independently of the surface characteristics of the sheet metal parts, gives good strength i values with a cohesive fracture.
i This problem is solved by a metal-bonding adhesive in the form of a plastisol of the aforementioned type, which as the primer contains a polyether carrying hydroxy and primary and/or secondary amino substituents.
advantage that it undergoes initial gelling at low temperatu S(approximately 100 C) and already has an adequate ad ve strength. Thus, during the subsequent working of the sheet parts right up to the stoving cycle, the metal-bonding a ve coating is not damaged, i.e. it is not for example washed y by washing fluids.
Products su e as primers according to the inivention are commerci, y available. These products have hitherto been used as m epoxy -T r-uimert.- 2a Thus, according to the present invention, there is provided a metal-bonding adhesive in the form of a plastisol formed from an acrylic resin having heterocyclic groups with at least one N-atom in the ring, plasticizers, a primer and optionally inert fillers, as well as further additives, characterized in that it contains a polyether carrying hydroxy and primary and/or secondary amino substituents as the primer.
The metal-bonding adhesive according to the invention has the further advantage that it undergoes izitial gelling at low temperatures (approximately 100 C) and already has an adequate adhesive strength.
seas Thus, during the subsequent working of the sheet metal parts right up to 6o0 *the stoving cycle, the metal-bonding adhesive coating is not damaged, Sa 4 o it is not for example washed away by washing fluids.
Products suitable as primers according to the invention are commercially available. These products have hitherto been used as hardeners for epoxy resins and as crosslinking agents of a primer for ee o *s 0 e 6 -3 PVC- plastisols. It could not be concluded therefrom that they would be suitable as primers for the acrylic resin- based metal-bonding adhesive according to the invention.
Such polyethers,which carry hydroxy and primary and/or secondary amino substituents, are e.g. obtainable in that an epoxy resin is reacted with at least one mol of amine per epoxy equivalent. Along its chain, the thus obtained polyether carries hydroxy groups and has amino substituents at its ends. However, the invention is not restricted to this specific distribution of the substituents.
Within the scope of the present invention, the term primary or secondary amino substituents is used for substitution products of ammonia, in which one or two H- atoms of NH 3 are replaced by alkyl or aryL radicals.
r Examples of such groups are obtained in ethylamine and diethylamine.
However, this term does not cover other types of nitrogen functions, such as amide, cyanide, nitro, nitroso, ureido or guanidino substituents.
For characterizing preferred forms of the primer according to the invention, it is appropriate to use as a basis the aforementioned preparation possibility which, is preferred as a result of the availability of epoxy resins. In particular araliphatic epoxy resins are t suitable for the said reaction, e.g. those based on bisphenol A. As IC4 amino components, preference is given to low molecular weight aliphatic polyamines, particularly ethylenediamine and diethylenetriamine, ethylenediamine being particularly preferred.
The primers accorAing to the invention are generally suitable for imprcvlng the adhesion properties of plastisols of the aforementioned type, i.e. random plastisols based on acrylic resins, which have heterocyclic groups with at least one N- atom in the ring. However, from the numerous possible combinations, the combination of a polymethylmethacrylate -4 having imidazole groups as the acrylic resin component with a primer has proved particularly appropriate and is obtainable by reacting an araliphatic epoxy resin based on bisphenol A with at least one mol of ethylenediamne per epoxy equivalent.
The primer, is incorporated into the metal-bonding adhesive according to the invention in the quantities conventionally used in the case of plastisols, i.e. 1 to 50, preferably 10 to 25 parts by weight of primer per 100 parts of acrylic resin are used. Based on 100 parts by weight of acrylic resin, the plastisol also contains to 800 parts of organic plasticizer and optionally up to 700 parts of inert fillers, as well as other additives.
The invention is illustrated hereinafter by means of examples.
In the examples, for the formulation of the adhesives according to the invention, a primer is used such as is obtainable by reacting an epoxy resin based on bisphenol A with an ethylenediamine excess. On the basis of analytical investigations, particularly H- NMR, 1C- NMR and IR- spectroscopy, the following structure can be associated with the main part of this primer: t CCH CCH-H
SOCHCH
I
I
I
I
C Ha, CH H I
I
1 Cu 1 I in which n is mainly 2. N N
N
H
The strength values given in the examples were mainly determined as tensile and shear strength values. The coating thickness of the in each case tested bond was 0.3 mm.
In order to determine the adhesive strength, a material bead was applied to the surface to be investigated and stoved at the given temperature. After cooling to ambient temperature, the adhesive strength was tested manually by means of a knife. An assessment scale of 0 to 10 was used for evaluation purposes, O indicating no adhesion and 10 very good adhesion. Of the intermediate values, represents adequate adhesion for subsequent working or processing.
9 0 Example 1 0 a0 o 6 A metal-bonding adhesive was prepared from the following .o constituents: polymethylmethacrylate copolymer with imidazole groups 20.00% by weight 0 0 0 dinonyl phthalate 33.40% by weight S" calcium oxide 2.00% by weight barite 27.00% by weight Sgraphite 15.00% by weight wetting agent 0.10% by weight primer 2.50% by weight For testing the adhesive strength, a material bead of this plastisol was applied to a rough or blank car body sheet and was stoved for 10 minutes at 90 C. The adhesion was evaluated 5. The test was repeated with a difference thai stoying took place for minutes at 1800C. Under otherwise identical conditions, an adhesive strength rating of 10 was now obtained.
I 6 Example 2 A metal-bonding adhesive was prepared from the following constituents: polymethylmethacrylate copolymer with imidazole groups 20.00% by weight dinonyl phthalate 33.40%. by weight calcium oxide 2.00%. by weight barite 27.00%. by weight titanium dioxide 15.00%. by weight wetting agent 0.10%. by weight primer 2.50%. by weight The adhesive strength was tested on a blank car body sheet as in 4@ 0 example 1. After stoving for 10 minutes at 90 C an adhesive ;irength rated 5 was obtained. After stoving for 20 minutes at 180 0 C, an adhesive strength of 10 was obtained.
o Compared with example 1, it can be seeri that a replacement of the fillers or inert additives, in this case graphite by titanium dioxide, had no recognisable influence on the adhesive strength of the metalbonding adhesive.
b44.4:Examples 1 and 2 also make it clear that the metal-bonding adhesives according to the invention undergo initial gelling at a relatively Low temperature and then have an adequate adhesive strength for further processing.
-7 Example 3 A metal-bonding adhesive was prepared from the following constituents: polymethylmethacrylate copolymer with imidazole groups 20.00% by weight aromatic plasticizer 33.00% by weight calcium oxide 00% by weight chalk 42.50% by weight primer 2.50% by weight Initially the adhesive strength of this metal-bonding adhesive Swas again tested on a blank car body sheet, for which purpose a material bead was stoved for 12 minutes at 170°C. An adhesive strengthof rating 10 was determined.
This test was repeated under otherwise identical conditions on an electrolytically galvanized sheet and in this case an adhesive strength of 9 was obtained. The test repeated under otherwise identical conditions with hot- dip galvanized sheet once again gave a rating of 9.
Two blank car body sheet fragments were bonded together with this metal-bonding adhesive. For this purpose, the metal-bonding adhesive was applied between the two sheets, so that a surface of approximately 2 cm was covered with a coating thickness of 0.3 mm, which was followed by stoving cycle lasting 20 minutes at 17000. The tensile and shear strength of this bond was determined as 280 N/am and a completely cohesive fracture was obtained. Thus, this metal bonding adhesive had excellent characteristics in connection with use on different metal sheets.
8 Example 4 A metal-bonding adhesive was prepared from the following constituents: polymethylmethacrylate copolymer with imidazole groups 22.00% by weight aromatic plasticizer 13.00% by weight Scumarone- indene resin 25.00% by weight calcium oxide 2.00% by weight chalk 25.00% by weight I
I
J graphite 10.00% by weight S primer 3.00% by weight It t Initially the adhesive strength of this metal-bonding adhesive 2 was tested on a car body sheet, coated with 12 g/m of a sheet bar.
wash oil. For this purpose a material bead was stoved for 22 minutes at 175 C giving an adhesive strength of This test was repeated under otherwise identical conditions with 2 a car body sheL; coated with 12 g/m of a deep drawing oil and once again the adhesive strength was rated 2 The test was repeated with a car body sheet coated with 12 g/m of a corrosion prevention oil and under otherwise identical conditions an adhesive strength of 10 was again obtained.
q The adhesive strength of the metal-bonding adhesive was tested on an uncoated blank car body sheet. For this test, a material bead was stoved for 20 minutes at 140 0 C and an adhesive strength of 10 was obtained.
The test was repeated under otherwise identical conditions with an electrolytically galvanized sheet and once again an adhesive strength of 10 was obtained.
-9 Two blank car body sheet portions were bonded together under the conditions of example 3. A tensile and shear strength of 2 427 N/cm was measured and the fracture was completely cohesive.
This example shows that the effectiveness of the metal-bonding adhesive according to the invention is not impaired by the various oily coatings, such as are e.g. used in the car industry. Thus, the metal-bonding adhesive according to the invention can be universally used and ensures excellent bonding.
Comparison Test 1 0. A comparison test was carried out in which the acrylic resin 900 0 component used was a polymethylmethacrylate copolymer conLining no 0 a heterocyclic groups with at least one N- atom in the ring. This 0 al o 9.
00 9comparison formulation was prepared from the following constituents: polymethylmethacrylate copolymer 20.00% by weight aromatic plasticizer 33.00. by weight calcium oxide 2.00% by weight o° ~>barite 42.50% by weight primer 2.50% by weight oo A material bead from this comparison formulation was applied to a blank car body sheet and was siubject to a 20 minute stoving cycle at 170 0 C. The adhesive strongth rating was 0.
This example makes it clear that it is important according to the invention that the metal-bonding adhesive contains an acrylic resin, which has heterocyclic groups with at least one N- atom in the ring.
Comparison Test 2 A further comparison formulation was prepared, using a polymethylmethacrylate copolymer with carboxyl groups: polymethylmethacrylate copolymer with carboxyl groups 20.00%. by weight dinonyl phthalate 33.00'. by weight calcium oxide 2.00%. by weight barite 42.50%. by weight primer 2.50%. by weight A material bead from this comparison formulation was applied to a blank car body sheet and underwent a 20 minute stoving cycle at 180 0C.
Th adeiesrnthwsrtd0 This example once again makes it clear that it is important according to the invention that the metal adhesive contains an acrylic resin, which contains heterocyclic groups with at least one N- atom in the ring.
Comparison Test 3 A further comparison formulation was prepared from the following constituents: ttPVC- homopolymer 18.007. by weight PVC- copolymer 2.00%/ by weight dioctyl phthalate 32.00% by weight bar ite 22.00%. by weight chalk 15.00. by weight calcium oxide 7 407. by weight titanium dioxide 0.507. by weight carbon black 0.-10. by weight primer 3.00%. by weight Smaterial bead from this comparison formulation was applied to a 11I blank car body sheet and underwent a 30 minute stoving cycle at 140 0
C.
The adhesive strength was rated 0.
This example also makes clear the significance of the inventive combination of acrylic resin and primer for the resulting adhesive strength on metal substrates.
Comparison Test 4 A comparison test was carried out without the primer according to the invention.
polymethylmethacrylate copolymer with imidazole groups 20.00% by weight aromatic plasticizer 33.00'/ by weight calcium oxide 2.00% by weight chalk 45.00% by weight The adhesive strength of this metal-bonding adhesive was firstly tested on a blank car body sheet, for which purposes a material bead was stoved for 12 minutes at 170 0 C. The adhesive strength was rated This test was repeated under otherwise identical conditions on an electrolytically galvanized sheet and in this case an adhesive strength of 9 was obtained.
This test was repeated under otherwise identical conditions on a hotdip galvanized sheet, where the adhesive strength was rated 0.
Two blank car body sheet portions were bonded together with this metal bonding adhesive. For this purpose, the metal-bonding adhesive was applied between the two sheets, so that a surface of 5 cm 2 wat c with a coating thickness of 0.3 mm. A stoving cycle lasting was then carried out at 170°C. The tensile and shear strength bond was determined as 206 N/cm A fracture was obtained, which wfl....
adhesive.
-12 This metal-bonding adhesive consequently had a lower adhesive strength and a lower tensile and shear strength than the metal bonding adhesive according to the invention.
Comparison Test A comparison test was carried out with the metal bonding adhesive of German patent 24 54 235.
polymethylmethacrylate copolymer with imidazole groups 20.00% by weight aromatic plasticizer 33.00% by weight calcium oxide 2.00% by weight :4 "chalk 42.25% by weight, o epoxy resin 2.50% by weight: 84 dicyandiamide 0.25%. by weight Initially the adhesive strength of this metal-bonding adhesive was 0404 tested on a blank car body sheet, for which purpose a material bead was 0 stoved for 12 minutes at 1700C. The adhesive strength was rated 0.
a °This test was repeated under otherwise identical conditions on an eloctrolytically galvanized sheet and in this case the qdhesive strength was rated QO The test repeated undier otherwise identical conditions with a hotdip gal,Anized sheet once again gave a O rating.
Tw o blank car body sheet portions were bonded together with this metal adhesive. For this purpose, the metal-bonding adhesive was applied 2 between the two sheets, so that a 5 cm surface was covered with a coating thickness of 0.3 mm. A 20 minute stoving cycle was then carried out at 170 0 C, The tensile and shear strength of this bond was found to be 2 237 N/cm A completely adhesive fracture was obtained.
2 I-13- Thus, this metal-bonding adhesive has an inferior adhesive strength and inferior tensile and shear strength when compared with the metal bonding adhesive according to the invention.
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Claims (8)
1. Metal-bonding adhesive in the form of a plastisol formed from an acrylic resin having heterocyclic groups with at least one N- atom in the ring, plasticizers, a primer and optionally inert fillers, as Swell as further additives, characterized in that it contains a poly- ether carrying hydroxy and primary and/or secondary amino substituents Sas the primer.
2. Metal-bonding adhesive according to Claim 1, characterized in that the primer is obtainable by reacting an epoxy resin with at least one mol of an aliphatic or aromatic amine per epoxy equivalent.
3. Metal-bonding adhesive according to Claim 2, characterized in that the primer is obtainable by reacting an epoxy resin with at least one mol of a low molecular weight, aliphatic polyamine per epoxy "l equivalent.
4. Metal-bonding adhesive according to either of the Claims 2 or 3, characterized in that the epoxy resin is an araliphatic epoxy resin.
Metal-bonding adhesive according to one of the Claims 2 to 4, characterized in that the polyamine is ethylenediamine or diethylene- triamine.
6. Metal-bonding adhesive according to one of the Claims 3 to characterized in that as the acrylic resin it has a polymethylmethacrylate having imidazole groups and a primer obtainable by reacting an araliphatic epoxy resin based on bisphenol A with at least one nol of ethylenediamine per epoxy equivalent.
7. Mecal-bonding adhesive according to one of the Claims 1 to 6, characterized in that it contains 1.0 to 50 parts by weight of primer per 100 parts of acrylic resin.
8. A metal-bonding adhesive, as claimed in Claim 1, substantially as hereinbefore described with reference to any one of the examples. C t DATED: 3 MAY 1990 TEROSON GmbH cBy their Patent Attorneys: PHILLIPS ORMONDE FITZPATRICK ,t1
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3523480 | 1985-07-01 | ||
| DE3523480A DE3523480C1 (en) | 1985-07-01 | 1985-07-01 | Metal adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU5750486A AU5750486A (en) | 1987-01-08 |
| AU599315B2 true AU599315B2 (en) | 1990-07-19 |
Family
ID=6274666
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU57504/86A Ceased AU599315B2 (en) | 1985-07-01 | 1986-05-16 | Metal bonding adhesive |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0209653B1 (en) |
| JP (1) | JPH0811789B2 (en) |
| AU (1) | AU599315B2 (en) |
| DE (2) | DE3523480C1 (en) |
| ES (1) | ES8900126A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4342672A1 (en) * | 1993-12-15 | 1995-06-22 | Akzo Nobel Nv | Adhesion improver |
| NL1010118C2 (en) * | 1998-09-17 | 2000-03-21 | Hoogovens Corporate Services B | Method for manufacturing a transition blank. |
| DE10130888A1 (en) | 2001-06-27 | 2003-01-30 | Henkel Teroson Gmbh | Adhesion promoter for plastisols |
| JP5965824B2 (en) * | 2012-11-26 | 2016-08-10 | 積水化学工業株式会社 | Post-curing tape and joining member joining method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1383217A (en) * | 1971-05-19 | 1975-02-05 | Basf Ag | Process for coating metal |
| US4210567A (en) * | 1974-11-15 | 1980-07-01 | Teroson G.M.B.H. | Plastisol of an acrylate polymer and a plasticizer |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2454235C3 (en) * | 1974-11-15 | 1982-01-07 | Teroson Gmbh, 6900 Heidelberg | Plastisols based on acrylate polymers |
| DE2529732C3 (en) * | 1975-07-03 | 1982-11-04 | Teroson Gmbh, 6900 Heidelberg | Plastisols based on acrylate polymers |
| GB1516510A (en) * | 1974-11-15 | 1978-07-05 | Teroson Gmbh | Plastisol of an organic polymer and a plasticiser |
-
1985
- 1985-07-01 DE DE3523480A patent/DE3523480C1/en not_active Expired
-
1986
- 1986-05-06 DE DE8686106177T patent/DE3664924D1/en not_active Expired
- 1986-05-06 EP EP86106177A patent/EP0209653B1/en not_active Expired
- 1986-05-16 AU AU57504/86A patent/AU599315B2/en not_active Ceased
- 1986-06-25 ES ES556597A patent/ES8900126A1/en not_active Expired
- 1986-06-26 JP JP61148344A patent/JPH0811789B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1383217A (en) * | 1971-05-19 | 1975-02-05 | Basf Ag | Process for coating metal |
| US4210567A (en) * | 1974-11-15 | 1980-07-01 | Teroson G.M.B.H. | Plastisol of an acrylate polymer and a plasticizer |
Also Published As
| Publication number | Publication date |
|---|---|
| ES556597A0 (en) | 1989-01-01 |
| JPH0811789B2 (en) | 1996-02-07 |
| EP0209653A1 (en) | 1987-01-28 |
| ES8900126A1 (en) | 1989-01-01 |
| EP0209653B1 (en) | 1989-08-09 |
| DE3664924D1 (en) | 1989-09-14 |
| DE3523480C1 (en) | 1987-01-22 |
| JPS624767A (en) | 1987-01-10 |
| AU5750486A (en) | 1987-01-08 |
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