Copolyamide adhesive.
Abstract
The invention relates to adhesive materials of copolyamides which can be processed at temperatures below 60 DEG C and are based on at least two polyamide-forming components which are distinguished in that they have a DSC melting point of at least 100 DEG C, a glass transition temperature of not more than 60 DEG C, measured by DSC on the dry powder, a softening temperature of at least 100 DEG C in the dry state and a softening temperature of below 100 DEG C after moistening with increasing weight and, after processing in a moist or moistened state, have heat distortion temperatures of at least 110 DEG C in an adhesive bond such as a high performance hotmelt adhesive. …<??>These materials have high adhesion values and high heat distortion temperatures but can be processed at low temperatures, in particular at room temperature, without it being necessary to admix environment- polluting solvents or tackifying additives.
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13 claims: 13 independent, 0 dependent
- 1Adhesives made from copolyamides, which can be processed at temperatures below 60 ° C, based on at least two polamide-forming components, characterized in that they have a DSC melting point of at least 100 ° C, a glass transition temperature, measured by DSC on dry powder, of at most 60 ° C, have a softening temperature of at least 100 ° C in the dry state and a softening temperature of less than 100 ° C after moistening while gaining weight and, after processing in a moist or humidified state, have heat resistance properties in the composite, such as high-performance hot melt adhesives of at least 100 ° C. 1. Klebemassen aus Copolyamiden, die bei Temperaturen unter 60°C verarbeitbar sind, auf der Basis von mindestens zwei polamidbildenden Komponenten, dadurch gekennzeichnet, daß sie einen DSC-Schmelzpunkt von mindestens 100°C, eine Glasübergangstemperatur, gemessen durch DSC am trockenen Pulver, von höchstens 60°C, in trockenem Zustand eine Erweichungstemperatur von mindestens 100°C sowie nach Befeuchten unter Gewichtszunahme eine Erweichungstemperatur unter 100°C besitzen und nach Verarbeiten in feuchtem bzw. befeuchteten Zustand Wärmestandfestigkeiten im Verbund wie Hochleistungsschmelzkleber von mindestens 100°C haben.
- 2Klebemassen nach Anspruch 1, dadurch gekennzeichnet, daß sie einen DSC-Schmelzpunkt zwischen 100 und 185°C, insbesondere zwischen 120 und 185°C, und eine Glasübergangstemperatur zwischen 0 und 60°C, insbesondere zwischen 25 und 60°C, besitzen. 2nd Adhesives according to claim 1, characterized in that they have a DSC melting point between 100 and 185 ° C, in particular between 120 and 185 ° C, and a glass transition temperature between 0 and 60 ° C, in particular between 25 and 60 ° C.
- 3Klebemassen nach Anspruch 1 und 2, dadurch gekennzeichnet, daß die Erweichungstemperatur, gemessen in trockenem Zustand, zwischen 110 und 160°C, und die Erweichungstemperatur, gemessen in feuchtem Zustand, zwischen 45 und 100°C liegt. 3rd Adhesives according to Claims 1 and 2, characterized in that the softening temperature, measured in the dry state, is between 110 and 160 ° C, and the softening temperature, measured in the moist state, is between 45 and 100 ° C.
- 4Klebemassen nach Anspruch 1 bis 3, dadurch gekennzeichnet, daß sie als Pulver nach einer Lagerung in Wasser mit einer Temperatur von 23°C während einer Zeitspanne von 16 Stunden einen Wassergehalt von mehr als 20 Gew.-%, insbesondere mehr als 25 Gew.-%, zeigen. 4th Adhesives according to Claims 1 to 3, characterized in that, after being stored in water at a temperature of 23 ° C, they have a water content of more than 20% by weight, in particular more than 25% by weight, for a period of 16 hours. %, demonstrate.
- 5Adhesives according to Claims 1 to 4, characterized in that, after processing in the moist state, they exhibit heat resistance in a bond of 130 to 180 ° C, in particular 140 to 160 ° C. 5. Klebemassen nach Anspruch 1 bis 4, dadurch gekennzeichnet, daß sie nach Verarbeitung in feuchtem Zustand Wärmestandfestigkeiten im Verbund von 130 bis 180°C, insbesondere 140 bis 160°C, zeigen.
- 6Adhesives according to claims 1 to 5, characterized. records that an essential polyamide-forming component is a salt or mixture of at least one diamine having 6 to 22 carbon atoms of the formula with n = 0 to 6, m = 0 to 6, x = 0 to 4 and at least one aliphatic dicarboxylic acid with 6 to 12 carbon atoms and / or at least one aliphatic diamine with 6 to 12 carbon atoms and at least one aromatic dicarboxylic acid with 8 to 10 carbon atoms is. 6. Klebemassen nach Anspruch 1 bis 5, dadurch gekenn-. zeichnet, daß eine wesentliche polyamidbildende Komponente ein Salz oder Gemisch mindestens eines Diamins mit 6 bis 22 C-Atomen der Formel mit n = 0 bis 6, m = 0 bis 6, x = 0 bis 4 und mindestens einer aliphatischen Dicarbonsäure mit 6 bis 12 Kohlenstoffatomen und/oder mindestens eines aliphatischen Diamins mit 6 bis 12 Kohlenstoffatomen und mindestens einer aromatischen Dicarbonsäure mit 8 bis 10 Kohlenstoffatomen ist.
- 7Adhesives according to Claim 6, characterized in that an essential polyamide-forming component is a salt or mixture of at least one diamine of the formula (1) with n = 1 or 2, m = 1 or 2 and x = 0 and adipic acid, azelaic acid, sebacic acid or dodecanedioic acid and / or is hexamethylenediamine and terephthalic acid, isophthalic acid or toluenedicarboxylic acid, in particular salts or mixtures of m-xylylenediamine and adipic acid and / or of hexamethylenediamine and isophthalic acid are suitable. 7. Klebemassen nach Anspruch 6, dadurch gekennzeichnet, daß eine wesentliche polyamidbildende Komponente ein Salz oder Gemisch mindestens eines Diamins der Formel (1) mit n = 1 oder 2, m = 1 oder 2 und x = 0 und Adipinsäure, Azelainsäure, Sebazinsäure oder Dodecandisäure und/oder Hexamethylendiamin und Terephthalsäure, Isophthalsäure oder Toluoldicarbonsäure ist, wobei insbesondere Salze oder Gemische aus m-Xylylendiamin und Adipinsäure und/oder aus Hexamethylendiamin und Isophthalsäure geeignet sind.
- 8Klebemassen nach Anspruch 6 oder 7, dadurch gekennzeichnet, daß die wesentliche polyamidbildende Kopmonente in einer Menge von 15 bis 55 Gew.-%, bezogen auf die Gesamtklebemasse, vorliegt. 8th. Adhesive compositions according to claim 6 or 7, characterized in that the essential polyamide-forming copolymer is present in an amount of 15 to 55% by weight, based on the total adhesive composition.
- 9Adhesives according to claims 1 to 7, characterized in that they contain, in addition to the essential polyamide-forming component of claim 6, at least one further conventional polyamide-forming component. 9. Klebemassen nach den Ansprüchen 1 bis 7, dadurch gekennzeichnet, daß sie neben der wesentlichen polyamidbildenden Komponente des Anspruchs 6 mindestens eine weitere übliche polyamidbildende Komponente enthalten.
- 10Klebemassen nach Anspruch 9, dadurch gekennzeichnet, daß die weitere polyamidbildende Komponente aus Gemischen aus aliphatischen Diaminen und Dicarbonsäuren mit 4 bis 12 Kohlenstoffatomen und/oder Lactamen und/oder ω-Aminocarbonsäuren mit 6 bis 12 Kohlenstoffatomen oder deren Gemischen besteht. 10th Adhesives according to claim 9, characterized in that the further polyamide-forming component consists of mixtures of aliphatic diamines and dicarboxylic acids with 4 to 12 carbon atoms and / or lactams and / or ω-aminocarboxylic acids with 6 to 12 carbon atoms or mixtures thereof.
- 11Adhesives according to Claim 10, characterized in that the additional polyamide-forming component consists of 1 to 50% by weight, in particular 1 to 40% by weight, hexamethylenediamine and adipic acid and adipic acid and 25 to 75% by weight, in particular 30 to 60% by weight .-%, caprolactam and / or ω-aminocaproic acid. 11. Klebemassen nach Anspruch 10, dadurch gekennzeichnet, daß die zusätzliche polyamidbildende Komponente aus 1 bis 50 Gew.-%, insbesondere 1 bis 40 Gew.-%, Hexamethylendiamin und Adipinsäure und Adipinsäure und 25 bis 75 Gew.-%, insbesondere 30 bis 60 Gew.-%, Caprolactam und/oder ω-Aminocapronsäure besteht.
- 13Use of the adhesive compositions according to claims 1 to 12 for the production of composite materials or as adhesive compositions by processing under the influence of moisture, such as water vapor, preferably at temperatures below 30 ° C, in particular room temperature. 13. Verwendung der Klebemassen nach den Ansprüchen 1 bis 12 zur Herstellung von Verbundmaterialien oder als Klebemassen durch Verarbeiten unter der Einwirkung von Feuchtigkeit, wie Wasserdampf, vorzugsweise bei Temperaturen unterhalb 30°C, insbesondere Raumtemperatur.
Independent claims13
34 paragraphs, as filed
The present invention relates to copolyamide adhesives whose processability and / or bondability is greatly improved or made possible by the action of moisture or water and whose heat resistance after processing is far above the temperature used for processing, namely in the area of so-called high-performance hotmelt adhesives.
It is known that caprolactam, laurolactam, hexamethylenediamine adipinate and other aliphatic polyamide formers are suitable for adhesives if the monomer composition is chosen so that the melting point of the copolyamide is about 70-150 ° C. Copolyamides of this type, as described in DE 12 53 449, DE 22 63 922, DE 23 24 159, DE 23 24 160, DE 32 48 766, DE 39 33 762, CH 491 150, CH 482 756 and CH 540 311 are, for example good wash and cleaning resistance as adhesives.
JP 79 923 397 describes copolyamides from caprolactam, laurolactam and m-xylylenediamine adipinate, which have a particularly good resistance to cleaning.
According to JP 74 019 093 there is good washing and cleaning resistance even with copolyamides from caprolactam and salts from m-xylylenediamine and dodecanedioic acid. Copolyamides of xylylenediamine and dimer fatty acids are also suitable as adhesives. (NL 17 45 63, NL 75 08 420, JP 81 029 687, CA 887 138).
All of these copolyamides are highly resistant to solvents in dry cleaning and water in laundry. The adhesive values and heat resistance of such polyamide hotmelt compositions are very high compared to other hotmelt adhesives, such as ethylene / vinyl acetate copolymers or styrene / butadiene block copolymers. They are therefore referred to as high-performance hot melt adhesives (F. Eichhorn and Th. Reiner, Elektro-Anzeiger 34/7, 33 (1981)).
The disadvantage of the copolyamide hotmelt adhesives described is that the high temperature required for processing is generally higher than the softening temperature of the copolyamides themselves. The heat resistance of the bond corresponds to the softening temperature of the copolyamides and is therefore lower than the temperature required for processing.
Low processing temperatures have those polymer compositions which contain additives with plasticizing or tackifying effects (US 37 92 002, US 34 49 273, US 37 87 342). However, the heat resistance of such polymer compositions is poorer for bonds than for polyamide adhesives without the additives mentioned. In addition, the adhesive values that can be achieved are lower than for copolyamide adhesives without additives.
It was therefore the task of creating adhesives with high adhesive values and high heat resistance which can be processed at low temperatures, if possible at room temperature, without admixing environmentally harmful solvents or tackifying additives.
This object is achieved according to the invention by adhesive compositions which can be processed at temperatures below 60 ° C, based on at least two polyamide-forming components, which compositions are characterized in that they measure a DSC melting point of at least 100 ° C, a glass transition temperature by DSC on dry powder, of at most 60 ° C, have a softening temperature of at least 100 ° C in the dry state and a softening temperature below 100 ° C after moistening with weight gain and, after processing in the moist or humidified state, have heat resistance properties in the composite, such as high-performance hot melt adhesives, of at least 110 ° C, the compositions according to the invention particularly after moistening can be processed at room temperature.
The invention is accordingly based on the finding that special copolyamides, when used in the moist state, allow processing far below their softening point. However, their heat resistance is given by the softening point. The adhesive values that can be achieved correspond to those of the so-called high-performance hot-melt adhesives described above. Compared to high-performance hot-melt adhesives, the copolyamides of the present invention thus have the clear and very special advantage that the temperature required for processing is far below the resulting heat resistance. Compared to conventional tackifying hotmelt adhesives, they have the advantage that no physically mixed, low-molecular components can migrate out, which pollute the environment. The main advantage, however, is that the heat resistance and adhesion values achieved are considerably higher than those that can be achieved with tackifying adhesives.
The advantageous properties of the copolyamides used in the adhesives according to the invention can be used in a variety of ways during processing, because the temperatures required for this can be kept low in a manner not previously known. In this way, the processing steps, in particular gluing, can be carried out in an energy-saving and product-friendly manner.
Suitable adhesive compositions according to the invention are copolyamides,<ul id="ul0001" list-style="none"><li>a) have the DSC melting points of at least 100 ° C., in particular between 120 and 185 ° C., the DSC melting points being measured on dry powders at a heating rate of 20 ° C./min,</li><li>b) whose glass transition temperatures are below 60 ° C, in particular between 25 and 60 ° C, the glass transition temperature being measured on dry powders, by first heating the powders above their melting points and then quenching them with dry ice, the glass transition temperatures being determined as the second heating the temperatures at which the slopes of the DSC curves change,</li><li>c) whose softening temperatures, measured with the Kofler bank on dry powders, are above 100 ° C., in particular between 110 and 160 ° C.,</li><li>d) which, when stored in water at a temperature of 23 ° C. for a period of 16 hours, has a water content (determined by Karl Fischer titration) of more than 20% by weight, in particular more than 25% by weight, accept,</li><li>e) whose softening temperatures, measured with the Kofler bench on moist powders, ie those with more than 20% by weight, in particular more than 25% by weight, of water, are below 100 ° C., in particular between 45 and 100 ° C. ,</li><li>f) processed in the moist state, below 60 ° C, in particular below 30 ° C, give composites that have heat resistance above 110 ° C, in particular between 130 and 180 ° C and very particularly between 140 and 160 ° C.</li></ul>
Copolyamides of the type according to the invention are preferably obtained when an essential polyamide-forming component consists of a salt or mixture of at least one diamine having 6 to 22 carbon atoms of the formula:<chemistry id="chem0001" num="0001"><img file="EP0306794A2_D0001.tif" /></chemistry> and at least one aliphatic dicarboxylic acid with 6 to 12 carbon atoms and / or from a salt or mixture of at least one aliphatic diamine with 6 to 12 carbon atoms and at least one aromatic dicarboxylic acid with 8 to 10 carbon atoms.
Preferred monomers of this polyamide-forming component are diamines with n = 1 or 2, m = 1 or 2, x = 0 and adipic acid, azelaic acid, sabacic acid or dodecanedioic acid and / or hexamethylenediamine and terephthalic acid, isophthalic acid or toluenedicarboxylic acid. Copolyamides which contain 15 to 55% by weight, based on the total adhesive, of a salt or mixture of m-xylylenediamine and adipic acid and / or of hexamethylenediamine and isophthalic acid are very particularly suitable.
The remaining 45 to 85% by weight of the adhesive compositions consist of the customary aliphatic polyamide-forming components. These can be lactams and / or ω-aminocarboxylic acids with 6 to 12 carbon atoms and salts or mixtures of aliphatic diamines with 4 to 12 carbon atoms, especially with 6 to 12 carbon atoms, and aliphatic dicarboxylic acids with 4 to 12, in particular with 6 to 12 carbon atoms, or mixtures of these polyamide-forming components.
Particularly suitable adhesives are produced from 1 to 50% by weight, particularly 1 to 40% by weight, based on the total adhesive, of a salt or mixture of hexamethylenediamine and adipic acid and 25 to 75% by weight, particularly 30 to 60 % By weight of caprolactam and / or ω-aminocaproic acid. The adhesives according to the invention are advantageously packaged into granules, powders, films or other customary forms.
For the application of an adhesive with the copolyamide adhesive according to the invention, the polymer mass, as is usual for hot melt adhesives, is applied as a powder, film or melt to one or both of the substrates to be bonded. Before the adhesive is applied, the polymer is moistened with water or steam. The two substrates to be bonded are then joined together. The assembly takes place at a temperature which is significantly below the softening temperature of the original, dry polyamide adhesive.
The assembly is preferably carried out at a temperature of less than 60 ° C., preferably below 30 ° C., and in particular at room temperature. After the bonded parts have dried, the bond has a heat resistance which is significantly higher than the temperature used for the bond. If it is moistened again, for example as before processing, the previous state set for processing, for example for gluing, can no longer be reached, ie the adhesive remains hard and its heat resistance remains in a range which is substantially above the temperature used for processing, preferably close to the softening point of the original dry adhesive. The adhesive strength is of the order of magnitude that is customary for high-performance hot melt adhesives based on copolyamide.
The solid state of the adhesive is only reversed at the softening point or by melting again. After that it is possible to start processing again with moisture. The following examples illustrate the use and the properties of the adhesives according to the invention. Comparative examples 7 and 8 serve to delimit the claimed range of the composition of the adhesives according to the invention. Comparative example 9 serves to delimit known copolyamide adhesives. Comparative examples 10 and 11 serve to delimit polyamide adhesives which are made tacky by means of additives.
Copolyamide production
Examples 1 to 6 and Comparative Examples 7 to 9
Caprolactam, hexamethylenediamine adipinate (AH salt) and m-xylenediamine adipinate (MXDA.6 salt), Hexamethylene diamine isophthalate (6th IPS salt) or aminolauric acid are weighed into a stainless steel reaction vessel. After the vessel has been closed, it is flushed with nitrogen. The reaction vessel is placed in a metal block heated to 180 ° C. After 15 min. Melting time, the monomer melt is stirred. After one hour, the mixture is heated to 250 ° C. with stirring. After a further five hours of reaction time, the reaction vessel is emptied. The copolyamide is then annealed at 70 ° C for 2 hours.
Composition of the adhesives (Table 1)
Properties of the adhesives (Table 2)
Comparative Example 10
50 Parts by weight of the copolyamide from Example 9 are, as described in US Pat. No. 3,787,342, formulated with 5 parts by weight of a glycerol ester of fumaric acid-modified rosin resin and 2.5 parts by weight of paraffin with a melting point of 55 ° C.
Comparative Example 11
As described in US Pat. No. 3,449,273, a copolyamide adhesive composed of 90% by weight of the copolyamide from Example 9 is mixed with 10% by weight naphthol.
Bonding with powder
(Table 3)
The copolyamides are ground using a pin mill at -80 ° C. A polyester needle felt with a weight of 200 g per square meter is coated from the raw material in a litter application in such a way that the adhesive layer is 50 g / m². The powder is sintered under an infrared radiator under as mild conditions as possible. Then the coated needle fleece, if "moist" is noted in the table below, is sprayed with water on the side coated with adhesive. The fleece is then glued in a flat press with a pressure of 2 kp / cm² using Tritex phenolic resin press plates. The peel adhesion according to DIN 45 310 and the heat resistance are then measured. To measure the heat resistance, test specimens of 2 x 8 cm are peeled with 0.4 N / 2 cm and at 1 ° C / min. heated up. The temperature at which the peel adhesion falls below 0.4 N / 2 cm applies as heat resistance.
Gluing with foil
(Table 4)
Films with a thickness of 50 µm are produced from the hot melt adhesives by pressing at elevated temperature. These adhesive films are used to bond polyester needle fleece to Tritex phenolic resin press plates. Gluing and testing are carried out in the same way as for powder.<tables id="tabl0001" num="0001"><table frame="all"><title>Table 1</title><tgroup cols="6" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="26.25mm" /><colspec colnum="2" colname="col2" colwidth="26.25mm" /><colspec colnum="3" colname="col3" colwidth="26.25mm" /><colspec colnum="4" colname="col4" colwidth="26.25mm" /><colspec colnum="5" colname="col5" colwidth="26.25mm" /><colspec colnum="6" colname="col6" colwidth="26.25mm" /><thead valign="top"><row><entry namest="col1" nameend="col6" align="center"><u style="single">Compositions</u></entry></row><row><entry namest="col1" nameend="col1" align="center">example</entry><entry namest="col2" nameend="col2" align="center">Caprolactam</entry><entry namest="col3" nameend="col3" align="center">AH salt</entry><entry namest="col4" nameend="col4" align="center">MXDA.6 salt</entry><entry namest="col5" nameend="col5" align="center">6.IPS salt</entry><entry namest="col6" nameend="col6" align="center">Aminolauric acid</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="center">% By weight</entry><entry namest="col3" nameend="col3" align="center">% By weight</entry><entry namest="col4" nameend="col4" align="center">% By weight</entry><entry namest="col5" nameend="col5" align="center">% By weight</entry><entry namest="col6" nameend="col6" align="center">% By weight</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="right">1</entry><entry namest="col2" nameend="col2" align="right">40</entry><entry namest="col3" nameend="col3" align="right">20</entry><entry namest="col4" nameend="col4" align="right">40</entry><entry namest="col5" nameend="col5" /><entry namest="col6" nameend="col6" /></row><row><entry namest="col1" nameend="col1" align="right">2</entry><entry namest="col2" nameend="col2" align="right">33</entry><entry namest="col3" nameend="col3" align="right">28</entry><entry namest="col4" nameend="col4" align="right">39</entry><entry namest="col5" nameend="col5" /><entry namest="col6" nameend="col6" /></row><row><entry namest="col1" nameend="col1" align="right">3</entry><entry namest="col2" nameend="col2" align="right">55</entry><entry namest="col3" nameend="col3" align="right">15</entry><entry namest="col4" nameend="col4" align="right">30</entry><entry namest="col5" nameend="col5" /><entry namest="col6" nameend="col6" /></row><row><entry namest="col1" nameend="col1" align="right">4</entry><entry namest="col2" nameend="col2" align="right">25</entry><entry namest="col3" nameend="col3" align="right">25</entry><entry namest="col4" nameend="col4" align="right">50</entry><entry namest="col5" nameend="col5" /><entry namest="col6" nameend="col6" /></row><row><entry namest="col1" nameend="col1" align="right">5</entry><entry namest="col2" nameend="col2" align="right">40</entry><entry namest="col3" nameend="col3" align="right">30</entry><entry namest="col4" nameend="col4" /><entry namest="col5" nameend="col5" align="right">30</entry><entry namest="col6" nameend="col6" /></row><row><entry namest="col1" nameend="col1" align="right">6</entry><entry namest="col2" nameend="col2" align="right">55</entry><entry namest="col3" nameend="col3" align="right">15</entry><entry namest="col4" nameend="col4" align="right">10</entry><entry namest="col5" nameend="col5" align="right">20</entry><entry namest="col6" nameend="col6" /></row><row><entry namest="col1" nameend="col1" align="right">7</entry><entry namest="col2" nameend="col2" align="right">20</entry><entry namest="col3" nameend="col3" align="right">46</entry><entry namest="col4" nameend="col4" align="right">34</entry><entry namest="col5" nameend="col5" /><entry namest="col6" nameend="col6" /></row><row><entry namest="col1" nameend="col1" align="right">8</entry><entry namest="col2" nameend="col2" align="right">60</entry><entry namest="col3" nameend="col3" align="right">30</entry><entry namest="col4" nameend="col4" align="right">10</entry><entry namest="col5" nameend="col5" /><entry namest="col6" nameend="col6" /></row><row rowsep="1"><entry namest="col1" nameend="col1" align="right">9</entry><entry namest="col2" nameend="col2" align="right">60</entry><entry namest="col3" nameend="col3" align="right">20</entry><entry namest="col4" nameend="col4" /><entry namest="col5" nameend="col5" /><entry namest="col6" nameend="col6" align="right">20</entry></row></tbody></tgroup></table></tables><tables id="tabl0002" num="0002"><table frame="all"><title>Table 2</title><tgroup cols="7" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="22.50mm" /><colspec colnum="2" colname="col2" colwidth="22.50mm" /><colspec colnum="3" colname="col3" colwidth="22.50mm" /><colspec colnum="4" colname="col4" colwidth="22.50mm" /><colspec colnum="5" colname="col5" colwidth="22.50mm" /><colspec colnum="6" colname="col6" colwidth="22.50mm" /><colspec colnum="7" colname="col7" colwidth="22.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col7" align="center"><u style="single">properties</u></entry></row><row><entry namest="col1" nameend="col1" align="center">example</entry><entry namest="col2" nameend="col2" align="center">DSC Schm.-Punkt</entry><entry namest="col3" nameend="col3" align="center">DSC glass transition</entry><entry namest="col4" nameend="col4" align="center">Adult pts. tro</entry><entry namest="col5" nameend="col5" align="center">Adult pts. storage</entry><entry namest="col6" nameend="col6" align="center">H₂O after storage</entry><entry namest="col7" nameend="col7" align="center">Stickiness moist</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="center">° C</entry><entry namest="col3" nameend="col3" align="center">° C</entry><entry namest="col4" nameend="col4" align="center">° C</entry><entry namest="col5" nameend="col5" align="center">° C</entry><entry namest="col6" nameend="col6" align="center">% By weight</entry><entry namest="col7" nameend="col7" /></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="right">1</entry><entry namest="col2" nameend="col2" align="right">126</entry><entry namest="col3" nameend="col3" align="right">33</entry><entry namest="col4" nameend="col4" align="right">133</entry><entry namest="col5" nameend="col5" align="right">73</entry><entry namest="col6" nameend="col6" align="right">28</entry><entry namest="col7" nameend="col7" align="left">sticks</entry></row><row><entry namest="col1" nameend="col1" align="right">2</entry><entry namest="col2" nameend="col2" align="right">139</entry><entry namest="col3" nameend="col3" align="right">53</entry><entry namest="col4" nameend="col4" align="right">141</entry><entry namest="col5" nameend="col5" align="right">77</entry><entry namest="col6" nameend="col6" align="right">52</entry><entry namest="col7" nameend="col7" align="left">sticks</entry></row><row><entry namest="col1" nameend="col1" align="right">3</entry><entry namest="col2" nameend="col2" align="right">138</entry><entry namest="col3" nameend="col3" align="right">36</entry><entry namest="col4" nameend="col4" align="right">142</entry><entry namest="col5" nameend="col5" align="right">81</entry><entry namest="col6" nameend="col6" align="right">55</entry><entry namest="col7" nameend="col7" align="left">sticks</entry></row><row><entry namest="col1" nameend="col1" align="right">4</entry><entry namest="col2" nameend="col2" align="right">175</entry><entry namest="col3" nameend="col3" align="right">57</entry><entry namest="col4" nameend="col4" align="right">134</entry><entry namest="col5" nameend="col5" align="right">90</entry><entry namest="col6" nameend="col6" align="right">29</entry><entry namest="col7" nameend="col7" align="left">sticks</entry></row><row><entry namest="col1" nameend="col1" align="right">5</entry><entry namest="col2" nameend="col2" align="right">121</entry><entry namest="col3" nameend="col3" align="right">26</entry><entry namest="col4" nameend="col4" align="right">110</entry><entry namest="col5" nameend="col5" align="right">49</entry><entry namest="col6" nameend="col6" align="right">27</entry><entry namest="col7" nameend="col7" align="left">sticks</entry></row><row><entry namest="col1" nameend="col1" align="right">6</entry><entry namest="col2" nameend="col2" align="right">141</entry><entry namest="col3" nameend="col3" align="right">54</entry><entry namest="col4" nameend="col4" align="right">128</entry><entry namest="col5" nameend="col5" align="right">60</entry><entry namest="col6" nameend="col6" align="right">31</entry><entry namest="col7" nameend="col7" align="left">sticks</entry></row><row><entry namest="col1" nameend="col1" align="right">7</entry><entry namest="col2" nameend="col2" align="right">157</entry><entry namest="col3" nameend="col3" align="right">39</entry><entry namest="col4" nameend="col4" align="right">160</entry><entry namest="col5" nameend="col5" align="right">124</entry><entry namest="col6" nameend="col6" align="right">32</entry><entry namest="col7" nameend="col7" align="left">" Not</entry></row><row><entry namest="col1" nameend="col1" align="right">8</entry><entry namest="col2" nameend="col2" align="right">157</entry><entry namest="col3" nameend="col3" align="right">25</entry><entry namest="col4" nameend="col4" align="right">149</entry><entry namest="col5" nameend="col5" align="right">102</entry><entry namest="col6" nameend="col6" align="right">31</entry><entry namest="col7" nameend="col7" align="left">" Not</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="right">9</entry><entry namest="col2" nameend="col2" align="right">144</entry><entry namest="col3" nameend="col3" align="right">21</entry><entry namest="col4" nameend="col4" align="right">140</entry><entry namest="col5" nameend="col5" align="right">92</entry><entry namest="col6" nameend="col6" align="right">31</entry><entry namest="col7" nameend="col7" align="left">" Not</entry></row></tbody></tgroup></table></tables><tables id="tabl0003" num="0003"><table frame="all"><title>Table 3</title><tgroup cols="5" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="31.50mm" /><colspec colnum="2" colname="col2" colwidth="31.50mm" /><colspec colnum="3" colname="col3" colwidth="31.50mm" /><colspec colnum="4" colname="col4" colwidth="31.50mm" /><colspec colnum="5" colname="col5" colwidth="31.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col5" align="center"><u style="single">Bonding with powder</u></entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="center">Adhesive from example</entry><entry namest="col2" nameend="col2" align="center">Status</entry><entry namest="col3" nameend="col3" align="center">Bonding temperature in ° C</entry><entry namest="col4" nameend="col4" align="center">Peel adhesion in N / 2cm</entry><entry namest="col5" nameend="col5" align="center">Heat resistance after processing ° C</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="right">1</entry><entry namest="col2" nameend="col2" align="left">wet</entry><entry namest="col3" nameend="col3" align="right">30</entry><entry namest="col4" nameend="col4" align="char" char=",">7,6</entry><entry namest="col5" nameend="col5" align="right">148</entry></row><row><entry namest="col1" nameend="col1" align="right">2</entry><entry namest="col2" nameend="col2" align="left">wet</entry><entry namest="col3" nameend="col3" align="right">30</entry><entry namest="col4" nameend="col4" align="char" char=",">6,9</entry><entry namest="col5" nameend="col5" align="right">154</entry></row><row><entry namest="col1" nameend="col1" align="right">3</entry><entry namest="col2" nameend="col2" align="left">wet</entry><entry namest="col3" nameend="col3" align="right">30</entry><entry namest="col4" nameend="col4" align="char" char=",">7,3</entry><entry namest="col5" nameend="col5" align="right">152</entry></row><row><entry namest="col1" nameend="col1" align="right">4</entry><entry namest="col2" nameend="col2" align="left">wet</entry><entry namest="col3" nameend="col3" align="right">30</entry><entry namest="col4" nameend="col4" align="char" char=",">7,5</entry><entry namest="col5" nameend="col5" align="right">140</entry></row><row><entry namest="col1" nameend="col1" align="right">5</entry><entry namest="col2" nameend="col2" align="left">wet</entry><entry namest="col3" nameend="col3" align="right">30</entry><entry namest="col4" nameend="col4" align="char" char=",">6,4</entry><entry namest="col5" nameend="col5" align="right">135</entry></row><row><entry namest="col1" nameend="col1" align="right">6</entry><entry namest="col2" nameend="col2" align="left">wet</entry><entry namest="col3" nameend="col3" align="right">60</entry><entry namest="col4" nameend="col5" align="center">no liability</entry></row><row><entry namest="col1" nameend="col1" align="right">7</entry><entry namest="col2" nameend="col2" align="left">wet</entry><entry namest="col3" nameend="col3" align="right">60</entry><entry namest="col4" nameend="col5" align="center">no liability</entry></row><row><entry namest="col1" nameend="col1" align="right">8</entry><entry namest="col2" nameend="col2" align="left">wet</entry><entry namest="col3" nameend="col3" align="right">60</entry><entry namest="col4" nameend="col5" align="center">no liability</entry></row><row><entry namest="col1" nameend="col1" align="right">9</entry><entry namest="col2" nameend="col2" align="left">dry</entry><entry namest="col3" nameend="col3" align="right">30</entry><entry namest="col4" nameend="col5" align="center">no liability</entry></row><row><entry namest="col1" nameend="col1" align="right">9</entry><entry namest="col2" nameend="col2" align="left">wet</entry><entry namest="col3" nameend="col3" align="right">30</entry><entry namest="col4" nameend="col5" align="center">no liability</entry></row><row><entry namest="col1" nameend="col1" align="right">9</entry><entry namest="col2" nameend="col2" align="left">dry</entry><entry namest="col3" nameend="col3" align="right">150</entry><entry namest="col4" nameend="col4" align="char" char=",">1,3</entry><entry namest="col5" nameend="col5" align="right">135</entry></row><row><entry namest="col1" nameend="col1" align="right">9</entry><entry namest="col2" nameend="col2" align="left">wet</entry><entry namest="col3" nameend="col3" align="right">150</entry><entry namest="col4" nameend="col4" align="char" char=",">5,7</entry><entry namest="col5" nameend="col5" align="right">145</entry></row><row><entry namest="col1" nameend="col1" align="right">9</entry><entry namest="col2" nameend="col2" align="left">dry</entry><entry namest="col3" nameend="col3" align="right">165</entry><entry namest="col4" nameend="col4" align="char" char=",">6,5</entry><entry namest="col5" nameend="col5" align="right">151</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="right">9</entry><entry namest="col2" nameend="col2" align="left">wet</entry><entry namest="col3" nameend="col3" align="right">165</entry><entry namest="col4" nameend="col4" align="char" char=",">6,9</entry><entry namest="col5" nameend="col5" align="right">145</entry></row></tbody></tgroup></table></tables><tables id="tabl0004" num="0004"><table frame="all"><title>Table 4</title><tgroup cols="5" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="31.50mm" /><colspec colnum="2" colname="col2" colwidth="31.50mm" /><colspec colnum="3" colname="col3" colwidth="31.50mm" /><colspec colnum="4" colname="col4" colwidth="31.50mm" /><colspec colnum="5" colname="col5" colwidth="31.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col5" align="center"><u style="single">Gluing with foil</u></entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="center">Adhesive from example</entry><entry namest="col2" nameend="col2" align="center">Status</entry><entry namest="col3" nameend="col3" align="center">Bonding temperature in ° C</entry><entry namest="col4" nameend="col4" align="center">Peel adhesion in N / 2cm</entry><entry namest="col5" nameend="col5" align="center">Heat resistance after processing</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="right">1</entry><entry namest="col2" nameend="col2" align="left">wet</entry><entry namest="col3" nameend="col3" align="right">30</entry><entry namest="col4" nameend="col4" align="char" char=",">10,3*</entry><entry namest="col5" nameend="col5" align="right">148</entry></row><row><entry namest="col1" nameend="col1" align="right">2</entry><entry namest="col2" nameend="col2" align="left">wet</entry><entry namest="col3" nameend="col3" align="right">30</entry><entry namest="col4" nameend="col4" align="char" char=",">11,0*</entry><entry namest="col5" nameend="col5" align="right">155</entry></row><row><entry namest="col1" nameend="col1" align="right">3</entry><entry namest="col2" nameend="col2" align="left">wet</entry><entry namest="col3" nameend="col3" align="right">30</entry><entry namest="col4" nameend="col4" align="char" char=",">10.9*</entry><entry namest="col5" nameend="col5" align="right">159</entry></row><row><entry namest="col1" nameend="col1" align="right">10</entry><entry namest="col2" nameend="col2" align="left">dry</entry><entry namest="col3" nameend="col3" align="right">30</entry><entry namest="col4" nameend="col5" align="center">no liability</entry></row><row><entry namest="col1" nameend="col1" align="right">10</entry><entry namest="col2" nameend="col2" align="left">wet</entry><entry namest="col3" nameend="col3" align="right">30</entry><entry namest="col4" nameend="col5" align="center">no liability</entry></row><row><entry namest="col1" nameend="col1" align="right">10</entry><entry namest="col2" nameend="col2" align="left">dry</entry><entry namest="col3" nameend="col3" align="right">120</entry><entry namest="col4" nameend="col4" align="char" char=",">2,1</entry><entry namest="col5" nameend="col5" align="right">117</entry></row><row><entry namest="col1" nameend="col1" align="right">10</entry><entry namest="col2" nameend="col2" align="left">wet</entry><entry namest="col3" nameend="col3" align="right">120</entry><entry namest="col4" nameend="col4" align="char" char=",">2,2*</entry><entry namest="col5" nameend="col5" align="right">124</entry></row><row><entry namest="col1" nameend="col1" align="right">10</entry><entry namest="col2" nameend="col2" align="left">dry</entry><entry namest="col3" nameend="col3" align="right">135</entry><entry namest="col4" nameend="col4" align="char" char=",">9,6*</entry><entry namest="col5" nameend="col5" align="right">126</entry></row><row><entry namest="col1" nameend="col1" align="right">10</entry><entry namest="col2" nameend="col2" align="left">wet</entry><entry namest="col3" nameend="col3" align="right">135</entry><entry namest="col4" nameend="col4" align="char" char=",">10,2*</entry><entry namest="col5" nameend="col5" align="right">129</entry></row><row><entry namest="col1" nameend="col1" align="right">11</entry><entry namest="col2" nameend="col2" align="left">dry</entry><entry namest="col3" nameend="col3" align="right">30</entry><entry namest="col4" nameend="col5" align="center">no liability</entry></row><row><entry namest="col1" nameend="col1" align="right">11</entry><entry namest="col2" nameend="col2" align="left">wet</entry><entry namest="col3" nameend="col3" align="right">30</entry><entry namest="col4" nameend="col5" align="center">no liability</entry></row><row><entry namest="col1" nameend="col1" align="right">11</entry><entry namest="col2" nameend="col2" align="left">dry</entry><entry namest="col3" nameend="col3" align="right">110</entry><entry namest="col4" nameend="col4" align="char" char=",">1,3</entry><entry namest="col5" nameend="col5" align="right">105</entry></row><row><entry namest="col1" nameend="col1" align="right">11</entry><entry namest="col2" nameend="col2" align="left">wet</entry><entry namest="col3" nameend="col3" align="right">110</entry><entry namest="col4" nameend="col4" align="char" char=",">2,5</entry><entry namest="col5" nameend="col5" align="right">115</entry></row><row><entry namest="col1" nameend="col1" align="right">11</entry><entry namest="col2" nameend="col2" align="left">dry</entry><entry namest="col3" nameend="col3" align="right">125</entry><entry namest="col4" nameend="col4" align="char" char=",">10.1*</entry><entry namest="col5" nameend="col5" align="right">121</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="right">11</entry><entry namest="col2" nameend="col2" align="left">wet</entry><entry namest="col3" nameend="col3" align="right">125</entry><entry namest="col4" nameend="col4" align="char" char=",">9,8</entry><entry namest="col5" nameend="col5" align="right">116</entry></row></tbody></tgroup><tgroup cols="5" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="31.50mm" /><colspec colnum="2" colname="col2" colwidth="31.50mm" /><colspec colnum="3" colname="col3" colwidth="31.50mm" /><colspec colnum="4" colname="col4" colwidth="31.50mm" /><colspec colnum="5" colname="col5" colwidth="31.50mm" /><tbody valign="top"><row><entry namest="col1" nameend="col5" align="justify">* Substrate breakage of the phenolic resin press plate</entry></row></tbody></tgroup></table></tables>
2 sheets
Sheet 1 Sheet 2
Every citation, both ways
| Document | Relation | Office | Cited during |
|---|---|---|---|
| DE1253449B | Cites | Germany | Applicant |
| NL174563B | Cites | Netherlands (Kingdom of the) | Applicant |
| FR2212359A1 | Cites | France | Search report |
| FR2239491A1 | Cites | France | Search report |
| DE2263922A1 | Cites | Germany | Applicant |
| DE2263922A1 | Cites | Germany | Search report |
| DE2324159A1 | Cites | Germany | Applicant |
| DE2324160A1 | Cites | Germany | Applicant |
| DE2729502A1 | Cites | Germany | Search report |
| DE3248776A1 | Cites | Germany | Applicant |
| US3449273A | Cites | United States of America | Applicant |
| US3787342A | Cites | United States of America | Applicant |
| US3792002A | Cites | United States of America | Applicant |
| DE3933762A1 | Cites | Germany | Applicant |
| CH482756A | Cites | Switzerland | Applicant |
| CH491150A | Cites | Switzerland | Applicant |
| CH540311A | Cites | Switzerland | Applicant |
| NL7508420A | Cites | Netherlands (Kingdom of the) | Applicant |
| GB799762A | Cites | United Kingdom | Search report |
| CA887138A | Cites | Canada | Applicant |
| JPS4919093A | Cites | Japan | Applicant |
| JPS4923397A | Cites | Japan | Applicant |
| JPS5629687A | Cites | Japan | Applicant |
11 members in 8 offices
Priority claims4
| Document | Office | Kind | Date |
|---|---|---|---|
| 347287 | Switzerland | A | |
| 47287 | Switzerland | – | |
| 47287 | – | – | – |
| CH19870003472 | – | – | – |
Members11
| Document | Office | Kind | |
|---|---|---|---|
| EP0306794A2This record | European Patent Office (EPO) | A2 | |
| JPH01103679A | Japan | A | |
| KR890005238A | Republic of Korea | A | |
| CH674518A5 | Switzerland | A5 | |
| US4943625A | United States of America | A | |
| EP0306794A3 | European Patent Office (EPO) | A3 | |
| EP0306794B1 | European Patent Office (EPO) | B1 | |
| AT83792T | Austria | T | |
| DE3876906D1 | Germany | D1 | |
| ES2053651T3 | Spain | T3 | |
| KR970005978B1 | Republic of Korea | B1 |
39 legal events, as 4 offices reported them to INPADOC
Over the term
Point at a mark for the eventEvents
| Event | Code | Office | |
|---|---|---|---|
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Announcement of lapse in spainLapsedFD2A | FD2A | ES | |
| Notification of lapseLapsedST | ST | FR | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Nl: lapsed or anulled due to non-payment of the annual feeLapsedNLV4 | NLV4 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Gb: european patent ceased through non-payment of renewal feeCeasedGBPC | GBPC | EP | |
| Patent ceasedCeasedPL | PL | CH | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP | PGFP | EP | |
| Definitive protectionFG2A | FG2A | ES | |
| No opposition filedOpposition26N | 26N | EP | |
| No opposition filed within time limitOppositionORIGINAL CODE: 0009261PLBE | PLBE | EP | |
| Information on the status of an ep patent application or granted ep patentGrantedSTATUS: NO OPPOSITION FILED WITHIN TIME LIMITSTAA | STAA | EP | |
| Gb: translation of ep patent filed (gb section 77(6)(a)/1977)GBT | GBT | EP | |
| Corresponds to:REF | REF | EP | |
| It: translation for a ep patent filedITF | ITF | EP | |
| It: translation for a ep patent filedITF | ITF | EP | |
| Fr: translation filedET | ET | EP | |
| Designated contracting statesAK | AK | EP | |
| Corresponds to:REF | REF | EP | |
| (expected) grantORIGINAL CODE: 0009210GRAA | GRAA | EP | |
| First examination report despatched17Q | 17Q | EP | |
| Request for examination filed17P | 17P | EP | |
| Designated contracting statesAK | AK | EP | |
| Search report despatchedORIGINAL CODE: 0009013PUAL | PUAL | EP | |
| Designated contracting statesAK | AK | EP | |
| Public reference made under article 153(3) epc to a published international application that has entered the european phaseORIGINAL CODE: 0009012PUAI | PUAI | EP |
Numbers
- Publication
- 0306794
- Publication, DOCDB
- 0306794
- Publication, EPODOC
- EP0306794
- Application
- 88114068
- Application, DOCDB
- 88114068
- Application, EPODOC
- EP19880114068
Titles3
- German
- Copolyamid Klebemassen
- English
- Copolyamide adhesive
- French
- Adhésif à base de copolyamide
Classification
- CPC, 2
- C08G69/26
- C08G69/265
- IPC, 4
- C08G69 00
- C08G69 26
- C09J177 00
- C09J177 10
Designated states9
- Contracting states, 9
- Austria
- Switzerland
- Germany
- Spain
- France
- United Kingdom
- Italy
- Liechtenstein
- Netherlands (Kingdom of the)