Solutions of polycondensates which contain N-heterocycles as structural units and show good adhesion on inorganic substrates.
Abstract
Solutions of polycondensates which have heterocyclic ring systems with N atoms as structural units, or solutions of precursors of these polycondensates in organic solvents containing 0.1 to 20% by weight, based on the polycondensates or their precursors, of at least one azidosilane of the general formula N₃-R³-Si-R¹n(OR²)3-n I. wherein R¹ is a C₁-C₃-alkyl, phenyl, benzyl or toluyl group, R² is a C₁-C₄-alkyl, C₂-C₄-alkoxyalkyl, phenyl or benzyl group, R³ is a C₁-C₈- Alkylene group which can be interrupted by an oxygen atom, sulfur atom or a - (N-R⁴) group, in which R⁴ represents a hydrogen, a methyl, ethyl or phenyl group, and n stands for 0.1 or 2.

Term
Term ended
Projected expiry passed 27 February 2012, 14.6 years ago.
- Priority
- Filed
- Published
- Projected expiry
- Today
7 claims: 3 independent, 4 dependent
- 1Lösungen von Polykondensaten, welche als Struktureinheiten heterocyclische Ringsysteme mit N-Atomen aufweisen, oder Lösungen von Vorstufen dieser Polykondensate in organischen Lösungsmitteln, enthaltend 0,1 bis 20 Gew.-%, bezogen auf die Polykondensate oder deren Vorstufen, mindestens eines Azidosilans der allgemeinen Formel N₃-R³-Si-R¹ n (OR²) 3-n I worin R¹ für eine C₁-C₃-Alkyl-, eine Phenyl-, Benzyl- oder Toluyl-gruppe, R² für eine C₁-C₄-Alkyl-, C₂-C₄-Alkoxyalkyl-, eine Phenyl- oder Benzylgruppe, R³ für eine C₁-C₈-Alkylengruppe, welche durch ein Sauerstoffatom, Schwefelatom oder eine -(N-R⁴)-Gruppe, worin R⁴ ein Wasserstoff, eine Methyl-, Ethyl- oder Phenylgruppe bedeutet, unterbrochen sein kann, und n für 0,1 oder 2 steht.
- 2Lösungen gemäß Anspruch 1, wobei es sich bei den Polykondensaten um Polyimide oder Polyamidsäuren als deren Vorstufe handelt.
- 3Lösungen gemäß Anspruch 1, enthaltend ein Azidosilan der allgemeinen Formel I, worin R² für eine C₁-C₄-Alkylgruppe und R³ für eine C₁-C₆-Alkylengruppe steht und n=0 ist.
- 4verfahren zur Verbesserung der Haftung von Polykondensaten, welche als Struktureinheiten heterocyclische Ringsysteme mit N-Atomen aufweisen, auf anorganischen Substraten, dadurch gekennzeichnet, daß den Lösungen der Polykondensate oder Lösungen von Vorstufen der Polykondensate in organischen Lösungsmitteln Azidosilane der allgemeinen Formel I zugesetzt werden und die erhaltenen Lösungen auf die anorganischen Substrate aufgetragen werden.
- 5Verwendung von Lösungen gemäß mindestens einem der Ansprüche 1 bis 3 zur Beschichtung von anorganischen Substraten.
- 6Verwendung gemäß Anspruch 5, wobei es sich bei den anorganischen Substraten um Substrate aus Silicium, Siliciumdioxid oder Siliciumnitrid handelt.
- 7Mit Polykondensaten, welche als Struktureinheiten heterocyclische Ringsysteme mit N-Atomen aufweisen, beschichtete anorganische Substrate, erhältlich unter Verwendung einer Lösung gemäß mindestens einem der Ansprüche 1 bis 3 oder hergestellt gemäß Anspruch 4.
Independent claims7
56 paragraphs, as filed
0001The invention relates to solutions of polycondensates which have heterocyclic ring systems with N atoms as structural units, or solutions of precursors of these polycondensates in organic solvents containing 0.1 to 20% by weight, based on the polycondensates or their precursors, of at least one azidosilane the general formula N₃-R³-Si-R¹<sub>n</sub>(OR²)<sub>3-n</sub> I. wherein R¹ is a C₁-C₃-alkyl, phenyl, benzyl or toluyl group, R² is a C₁-C₄-alkyl, C₂-C₄-alkoxyalkyl, phenyl or benzyl group, R³ is a C₁-C₈- Alkylene group which can be interrupted by an oxygen atom, sulfur atom or a - (N-R⁴) group, in which R⁴ represents a hydrogen, a methyl, ethyl or phenyl group, and n stands for 0.1 or 2.
0002Polyimides are increasingly used for coatings on metal wires, glass and quartz fibers, as well as substrates made of silicon, possibly with modified surfaces made of silicon dioxide or nitride, since the requirements for the temperature resistance of such coatings, for example in electronics and microelectronics, are constantly increasing are.
0003In order to ensure adequate adhesion of polyimide coatings, the inorganic substrates must be pretreated with so-called adhesion promoters. Aminoalkoxysilanes which are applied to the inorganic substrate in the form of their dilute alcoholic or alcoholic / aqueous solutions are usually used as adhesion promoters.
0004After removing the solvent, the polyimide or its soluble precursors can only be applied in a further step.
0005In addition to aminoalkoxysilanes, azidosilanes are also of interest as adhesion promoters.
0006US Pat. No. 3,705,911 describes silyl azide formats which are used to improve the adhesion of polymers to inorganic substrates.
0007Similar azido formats are known as adhesion promoters from GB-B-1 377 214 and GB-B-1 516 193.
0008EP-B-50 768 relates to a process for the preparation of azidosilanes of the general formula N₃-R³-Si-R¹<sub>n</sub>(OR²)<sub>3-n</sub>, where the radicals R¹ to R³ have the meaning given above and can represent, for example, short-chain alkyl or alkylene radicals.
0009The object of the present invention was to improve the adhesion of polyimides to inorganic substrates without the inorganic substrates having to be pretreated with an adhesion promoter.
0010Accordingly, the solutions defined above have been found.
0011The solutions according to the invention contain polycondensates which have heterocyclic ring systems with N atoms as structural units, or precursors of these polycondensates.
0012Possible polycondensates are, for example, polybenzimidazoles, polybenzothiazoles, polybenzoxazoles, polyoxazinediones, polyquinazolinediones, polyisoindoloquinazolinediones. Processes for the preparation of these polycondensates can be found, for example, in DE-A-29 33 826 and DE-A-23 11 659.
0013The polyoxazinediones are polycondensates with repeating structural units<chemistry id="chem0001" num="0001"><img file="EP0503376A2_D0001.tif" /></chemistry> which can be obtained by reacting dihydroxydicarboxylic acids and diisocyanates.
0014The polyquinazolinediones contain recurring structural units<chemistry id="chem0002" num="0002"><img file="EP0503376A2_D0002.tif" /></chemistry> and can be obtained by reacting diaminodicarboxylic acids and diisocyanates.
0015The polyisoindoloquinazolinediones have recurring structural units<chemistry id="chem0003" num="0003"><img file="EP0503376A2_D0003.tif" /></chemistry> and are available by reacting tetracarboxylic acid dianhydrides with o-aminoamides.
0016Recurring structural units in the polybenzoxazoles (thiazoles) are<chemistry id="chem0004" num="0004"><img file="EP0503376A2_D0004.tif" /></chemistry> The polybenzoxazoles (thiazoles) can be obtained, for example, by reacting dicarboxylic acids with di-o-aminophenols or thiophenols.
0017The polybenzimidazoles have recurring structural units<chemistry id="chem0005" num="0005"><img file="EP0503376A2_D0005.tif" /></chemistry> and arise in the reaction of di- (o-diamines) with dicarboxylic acids.
0018Preferred polycondensates with N-containing heterocyclic ring systems are polyimides with repeating structural units<chemistry id="chem0006" num="0006"><img file="EP0503376A2_D0006.tif" /></chemistry> which can be obtained, for example, by reacting tetracarboxylic acid dianhydrides with diamines or diisocyanates.
0019Precursors of the polyimides are also preferred. These precursors are polyamic acids with recurring structural units<chemistry id="chem0007" num="0007"><img file="EP0503376A2_D0007.tif" /></chemistry> in which the ring closure to the polyimide has not yet been completed.
0020At least one of the starting compounds from which the polycondensates or their precursors can be prepared preferably contains aliphatic carbon atoms. These can be aliphatic compounds, for example aliphatic diamines or diisocyanates, or aromatic compounds which have aliphatic carbon atoms, for example as alkyl or alkoxy substituents on aromatic ring systems or alkylene bridges between aromatic ring systems.
0021Particularly suitable tetracarboxylic acid dianhydrides, from which polyimides or polyamic acids are available, are those with a total of 8 to 20 carbon atoms for aliphatic and 10 to 20 carbon atoms for aromatic tetracarboxylic acid dianhydrides. Dianhydrides of aromatic tetracarboxylic acids, in particular of pyromellitic acid, 3,3 ', 4,4'-diphenyltetracarboxylic acid, 2,2'4,4'-diphenyltetracarboxylic acid, di (dicarboxydiphenyl) methanes, di (dicarboxydihydroxyphenyl) methanes or benzophenonetetracarboxylic acid are preferred.
0022Particularly suitable diamino compounds, from which polyimides or polyamic acids are available, have a total of 2 to 20 carbon atoms for aliphatic and 6 to 20 carbon atoms for aromatic diamino compounds. Aromatic diamino compounds are preferred, in particular 4,4'-diaminodiphenyl oxide, 3,3'-dimethylbenzidine, 3,3'-dimethoxibenzidine, 4,4'-diaminobenzophenone, 4,4'-diaminobiphenyl and 4,4'-isopropylenedianiline, diaminotoluenes, 4,4'-diaminodiphenylmethane and 2,2-bis-4 (4-aminophenoxy) phenylpropane.
0023Suitable or preferred diisocyanates for the production of polyimides are preferably diisocyanates corresponding to the diamines, which contain isocyanate groups instead of the amino groups. Diisocyanates which also contain amino groups in addition to the isocyanate groups, for example 9,9-bis (4-aminophenyl) fluorine diisocyanate, are also suitable.
0024In the event that both the diamino or diisocyanato compound and the tetracarboxylic anhydride are aromatic compounds as starting compounds for the polyimides or polyamic acids, preferably at least one of the starting compounds contains aliphatic carbon atoms, in particular as C₁-C₅ alkyl, alkoxy, Hydroxyalkyl substituents on an aromatic ring system or as a C₁-C₄ alkylene bridge between two aromatic ring systems.
0025The polycondensates or their precursors can also contain ethylenically unsaturated groups, so that the coatings can also be cured photochemically. For example, unsaturated alcohols such as allyl alcohol can be reacted with tetracarboxylic acid dianhydrides so as to bind unsaturated groups to the polymer.
0026In this case, a content of 0.01 to 2 mol, preferably 0.05 to 1.5 mol, of ethylenically unsaturated groups, based on 500 g of polycondensate or its precursors, has proven to be particularly suitable.
0027Another possibility of making the polycondensates or their precursors radiation-crosslinkable is the incorporation of benzophenone or its derivatives into the polymer structure. In the case of a desired photochemical crosslinking, the content of these carbonyl compounds is likewise 0.01 to 2 mol, preferably 0.05 to 1.5 mol, based on 500 g of polycondensate or its precursors.
0028The content of polycondensates with N-containing heterocyclic ring systems or their precursors in the solutions according to the invention is generally chosen so that the viscosity desired for processing is obtained. Concentrations between 5 and 80, in particular between 10 and 60% by weight have proven to be suitable.
0029Depending on the molecular weight and solubility of the polycondensates or their precursors, organic solvents of different polarity can be considered.
0030Phenolic solvents, for example cresol and amidic solvents, such as dimethylformamide, dimethylacetamide or N-methylpyrrolidone, have proven to be suitable solvents, in particular also for polyimides or polyamic acids.
0031The solutions according to the invention furthermore contain 0.1 to 20% by weight, preferably 0.2 to 10% by weight, particularly preferably 0.2 to 5% by weight, very particularly preferably 0.2 to 3% by weight , based on the polycondensates or their precursors of at least one azidosilane of the general formula N₃-R³-Si-R¹<sub>n</sub>(OR²)<sub>3-n</sub> I. wherein R¹ is a C₁-C₃-alkyl, phenyl, benzyl or toluyl group, R² is a C₁-C₄-alkyl, C₂-C₄-alkoxyalkyl, phenyl or benzyl group, R³ is a C₁-C₈- Alkylene group which can be interrupted by an oxygen atom, sulfur atom or a - (N-R⁴) group, in which R⁴ represents a hydrogen, a methyl, ethyl or phenyl group, and n stands for 0.1 or 2.
0032Aliphatic azidosilanes are preferred, in particular those in which R² is a C₁-C₄-alkyl group, R³ is a C₁-C₆-alkylene group and n = 0. 3-Azidopropyltriethoxysilane is very particularly preferred.
0033In addition, the solutions according to the invention can also contain alkanolamines which can further increase the adhesion to inorganic substrates. Alkanolamines of the general formula are particularly suitable (HO-R⁵-)<sub>m</sub>NH<sub>3 m</sub>where R⁵ is a C₁-C₆ alkylene radical and m = 1, 2 or 3. Their content is preferably between 0.1 to 5, particularly preferably between 0.2 to 2% by weight, based on the polycondensates or their precursors.
0034Furthermore, the solutions can contain, for example, conventional auxiliaries such as leveling agents, wetting agents, catalysts for curing, for example photoinitiators in the case of photochemical crosslinking, and stabilizers.
0035To prepare the solutions, the individual components can be dissolved in a suitable organic solvent or solvent mixture. The procedure can be such that the polycondensates or their precursors are first prepared in the organic solvent, for example polyimides or Polyamic acids are obtainable by reacting tetracarboxylic dianhydrides with diamino compounds, optionally in the presence of tertiary amines or organotin compounds, as catalysts in the polar solvents mentioned above. Then the azidosilanes and, if appropriate, further auxiliaries and additives can then be added to the solution.
0036An improvement in the adhesion effect can still be achieved if the solutions according to the invention are heated prior to their further processing.
0037A temperature of 40 to 100 ° C., in particular 50 to 70 ° C. for a period of 10 to 120, in particular 30 to 60 minutes, is suitable.
0038The solutions according to the invention are suitable for well-adhering coatings on inorganic substrates, for example on metals in the form of metal wires, glass and quartz fibers, and silicon (wafers). Adhesion to substrates based on silicon is particularly advantageous. In particular, very good adhesion of the coating can also be achieved on surface-modified silicon (silicon dioxide or silicon nitride surface by treatment with oxygen or nitrogen).
0039The inorganic substrates do not need to be pretreated with adhesion promoters, as was previously the case when using aminoalkoxysilanes.
0040After application, the solvent can be removed and, if necessary, the coating can be cured by increasing the temperature or by irradiation with high-energy light. After application, polyamic acids can be converted into polyimides by increasing the temperature.
Example 1: Polyamic acid solution
Preparation of the polyamic acid solution
00410.25 mol (102.75 g) of 2,2-bis (4- (4-aminophenoxy) phenylpropane was dissolved in 471.75 g of N-methylpyrrolidone at room temperature in a dry three-necked flask. This solution was heated to 50 ° C. under a gentle stream of dried nitrogen, then a total of 0.25 mol (54.5 g) of pyromellitic anhydride was stirred in in ten approximately equal portions at intervals of 10 minutes, stirring was continued for one hour at 60 ° C. and cooled to room temperature.
Production of varnishes L1 to L5 and V1 to V4
00423-Azidopropyltriethoxysilane (3AZPS) or 3-aminopropyltriethoxysilane (3AMPS) and diethanolamine (DEA) were added to the polyamic acid solution at room temperature (Table 1). The solution was kept at the temperature given in Table 1 for 1 hour after the adhesion promoter had been added, but before DEA was added.
exam
0043High-purity silicon wafers were oxidized to SiO₂ on their surface in oxygen plasma. The lacquers were spun onto these wafers using a spin coater, the speed of the spin coater being selected so that the coatings had a layer thickness of 10 ± 2 μm. The test specimens were dried at 90 ° C. for 30 minutes and the imidization of the polyamic acid was then carried out by heating to 350 ° C. for one hour.
0044The test specimens were then stored in a room climate for 48 hours and then boiled in demineralized water for 4 hours. Immediately after removal, the test specimens were dried, scratched with a sharp knife at 1 mm intervals and the adhesion was checked using Tesa film. The assessment was carried out according to an internal key, the grades 2 to 4 intermediate levels between grade 1 = perfect adhesion and grade 5 = residue-free delamination (table 1).<tables id="tabl0001" num="0001"><img file="EP0503376A2_D0008.tif" /></tables>
0045To test the storage stability, the paints were stored at room temperature and the time until the initial viscosity doubled was determined as a measure of the viscosity stability. To test the remaining adhesion-improving effect, adhesion tests were carried out on silicon wafers after 10 and 20 days as described above.<tables id="tabl0002" num="0002"><table frame="all"><title>Table 2</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="col1" align="center">paint</entry><entry namest="col2" nameend="col4" align="center">Adhesion to silicon wafers</entry><entry namest="col5" nameend="col5" align="center">Double the initial viscosity of the paint after</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="center">right after the paint is made</entry><entry namest="col3" nameend="col3" align="center">10th days later</entry><entry namest="col4" nameend="col4" align="center">20 days later</entry><entry namest="col5" nameend="col5" align="center">Weeks</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">L1</entry><entry namest="col2" nameend="col2" align="center">3</entry><entry namest="col3" nameend="col3" align="center">3</entry><entry namest="col4" nameend="col4" align="center">4</entry><entry namest="col5" nameend="col5" align="right">22</entry></row><row><entry namest="col1" nameend="col1" align="left">L2</entry><entry namest="col2" nameend="col2" align="center">2-3</entry><entry namest="col3" nameend="col3" align="center">2-3</entry><entry namest="col4" nameend="col4" align="center">3-4</entry><entry namest="col5" nameend="col5" align="right">22</entry></row><row><entry namest="col1" nameend="col1" align="left">L3</entry><entry namest="col2" nameend="col2" align="center">2</entry><entry namest="col3" nameend="col3" align="center">2</entry><entry namest="col4" nameend="col4" align="center">2-3</entry><entry namest="col5" nameend="col5" align="right">38</entry></row><row><entry namest="col1" nameend="col1" align="left">L4</entry><entry namest="col2" nameend="col2" align="center">1-2</entry><entry namest="col3" nameend="col3" align="center">2</entry><entry namest="col4" nameend="col4" align="center">3</entry><entry namest="col5" nameend="col5" align="right">12</entry></row><row><entry namest="col1" nameend="col1" align="left">L5</entry><entry namest="col2" nameend="col2" align="center">1</entry><entry namest="col3" nameend="col3" align="center">1</entry><entry namest="col4" nameend="col4" align="center">1-2</entry><entry namest="col5" nameend="col5" align="right">32</entry></row><row><entry namest="col1" nameend="col1" align="left">V1</entry><entry namest="col2" nameend="col2" align="center">5</entry><entry namest="col3" nameend="col3" align="center">5</entry><entry namest="col4" nameend="col4" align="center">5</entry><entry namest="col5" nameend="col5" align="right">34</entry></row><row><entry namest="col1" nameend="col1" align="left">V2</entry><entry namest="col2" nameend="col2" align="center">5</entry><entry namest="col3" nameend="col3" align="center">5</entry><entry namest="col4" nameend="col4" align="center">5</entry><entry namest="col5" nameend="col5" align="right">8</entry></row><row><entry namest="col1" nameend="col1" align="left">V3</entry><entry namest="col2" nameend="col2" align="center">5</entry><entry namest="col3" nameend="col3" align="center">5</entry><entry namest="col4" nameend="col4" align="center">5</entry><entry namest="col5" nameend="col5" align="right">10</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">V4</entry><entry namest="col2" nameend="col2" align="center">5</entry><entry namest="col3" nameend="col3" align="center">5</entry><entry namest="col4" nameend="col4" align="center">5</entry><entry namest="col5" nameend="col5" align="right">8</entry></row></tbody></tgroup></table></tables>
Example 2: Polyimide solution
Preparation of the polyimide solution
00460.25 mol (80.5 g) of bezophenonetetracarboxylic acid dianhydride were dissolved in 254 g of N-methylpyrrolidone (NMP) at room temperature in a dry three-necked flask. The mixture was heated to 70 ° C. under dried nitrogen, then a solution of 0.25 mol (101 g) of 9.9-bis (4-aminophenyl) fluoro diisocyanate in 254 g of NMP was added dropwise in the course of 2 hours; gas evolution started. After the end of the feed, the solution was kept at 140 ° C. for one hour and then cooled.
0047A brown resin solution was obtained. The acid number was 7. A spread on potassium bromide showed the band typical of PI in the IR spectrum at 1770 cm -1.
Production of paints L6 to L11 and V5 to V7 and testing of the paints
0048The paints were produced and the adhesion test was carried out as already described above. Table 3 lists the weight proportions of the adhesion promoter and the results of the adhesion test. After the adhesion promoter had been added, the solution was optionally kept at the temperature likewise given in Table 3 for one hour.<tables id="tabl0003" num="0003"><img file="EP0503376A2_D0009.tif" /></tables>
0049The liability remaining after storage was also checked as described above. <tables id="tabl0004" num="0004"><table frame="all"><title>Table 4</title><tgroup cols="4" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="39.37mm" /><colspec colnum="2" colname="col2" colwidth="39.37mm" /><colspec colnum="3" colname="col3" colwidth="39.37mm" /><colspec colnum="4" colname="col4" colwidth="39.37mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="center">paint</entry><entry namest="col2" nameend="col4" align="center">Adhesion to silicon wafers</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="center">right after the paint is made</entry><entry namest="col3" nameend="col3" align="center">10th days later</entry><entry namest="col4" nameend="col4" align="center">20 days later</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">L6</entry><entry namest="col2" nameend="col2" align="center">3</entry><entry namest="col3" nameend="col3" align="right">3</entry><entry namest="col4" nameend="col4" align="center">4</entry></row><row><entry namest="col1" nameend="col1" align="left">L7</entry><entry namest="col2" nameend="col2" align="center">2</entry><entry namest="col3" nameend="col3" align="right">2</entry><entry namest="col4" nameend="col4" align="center">2-3</entry></row><row><entry namest="col1" nameend="col1" align="left">L8</entry><entry namest="col2" nameend="col2" align="center">1-2</entry><entry namest="col3" nameend="col3" align="right">2</entry><entry namest="col4" nameend="col4" align="center">2-3</entry></row><row><entry namest="col1" nameend="col1" align="left">L9</entry><entry namest="col2" nameend="col2" align="center">1</entry><entry namest="col3" nameend="col3" align="right">1</entry><entry namest="col4" nameend="col4" align="center">1</entry></row><row><entry namest="col1" nameend="col1" align="left">L10</entry><entry namest="col2" nameend="col2" align="center">3</entry><entry namest="col3" nameend="col3" align="right">3</entry><entry namest="col4" nameend="col4" align="center">4</entry></row><row><entry namest="col1" nameend="col1" align="left">L11</entry><entry namest="col2" nameend="col2" align="center">1</entry><entry namest="col3" nameend="col3" align="right">1</entry><entry namest="col4" nameend="col4" align="center">1</entry></row><row><entry namest="col1" nameend="col1" align="left">V5</entry><entry namest="col2" nameend="col2" align="center">5</entry><entry namest="col3" nameend="col3" align="right">5</entry><entry namest="col4" nameend="col4" align="center">5</entry></row><row><entry namest="col1" nameend="col1" align="left">V6</entry><entry namest="col2" nameend="col2" align="center">5</entry><entry namest="col3" nameend="col3" align="right">5</entry><entry namest="col4" nameend="col4" align="center">5</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">V7</entry><entry namest="col2" nameend="col2" align="center">5</entry><entry namest="col3" nameend="col3" align="right">5</entry><entry namest="col4" nameend="col4" align="center">5</entry></row></tbody></tgroup></table></tables>
9 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6 Sheet 7 Sheet 8 Sheet 9
Every citation, both ways
| Document | Relation | Office | Cited during |
|---|---|---|---|
| EP0304022A2 | Cites | European Patent Office (EPO) | Search report |
| GB1516193A | Cites | United Kingdom | Search report |
| JPH0312346A | Cites | Japan | Examiner |
3 priority claims, no other members on record
Priority claims3
| Document | Office | Kind | Date |
|---|---|---|---|
| 4107664 | Germany | – | |
| 4107664 | Germany | A | |
| DE19914107664 | – | – | – |
42 legal events, as 3 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 | |
| Gb: european patent ceased through non-payment of renewal feeCeasedGBPC | GBPC | 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 | |
| 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 | |
| Se: european patent has lapsedLapsedEUG | EUG | EP | |
| Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25 | PG25 | EP | |
| Be: lapsedLapsedBERE | BERE | 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 | |
| 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 | |
| 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 | |
| Fr: translation filedET | ET | EP | |
| Gb: translation of ep patent filed (gb section 77(6)(a)/1977)GBT | GBT | EP | |
| Corresponds to:REF | REF | EP | |
| Designated contracting statesAK | AK | EP | |
| (expected) grantORIGINAL CODE: 0009210GRAA | GRAA | EP | |
| Despatch of communication of intention to grant a patentORIGINAL CODE: EPIDOS IGRAGRAH | GRAH | EP | |
| Despatch of communication of intention to grantORIGINAL CODE: EPIDOS AGRAGRAG | GRAG | EP | |
| Despatch of communication of intention to grant a patentORIGINAL CODE: EPIDOS IGRAGRAH | GRAH | EP | |
| Party data changed (applicant data changed or rights of an application transferred)RAP1 | RAP1 | EP | |
| Despatch of communication of intention to grantORIGINAL CODE: EPIDOS AGRAGRAG | GRAG | 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 | |
| Party data changed (applicant data changed or rights of an application transferred)RAP3 | RAP3 | 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
- 0503376
- Publication, DOCDB
- 0503376
- Publication, EPODOC
- EP0503376
- Application
- 921033130
- Application, DOCDB
- 92103313
- Application, EPODOC
- EP19920103313
Titles6
- German
- Lösungen von Polykondensaten, welche als Struktureinheiten N-enthaltende heterocyclische Ringsysteme aufweisen, mit verbesserter Haftung auf anorganischen Substraten
- English
- Solutions of polycondensates which contain N-heterocycles as structural units and show good adhesion on inorganic substrates
- French
- Solutions de polycondensats contenant comme unité structurale des N-hétérocycles et ayant une bonne adhésion sur des substrats inorganiques
- German
- Lösungen von Polykondensaten, welche als Struktureinheiten N-enthaltende heterocyclische Ringsysteme aufweisen, mit verbesserter Haftung auf anorganischen Substraten.
- English
- Solutions of polycondensates which contain N-heterocycles as structural units and show good adhesion on inorganic substrates.
- French
- Solutions de polycondensats contenant comme unité structurale des N-hétérocycles et ayant une bonne adhésion sur des substrats inorganiques.
Classification
- CPC, 3
- C08K5/544
- Y10T428/31663
- Y10T428/31721
- IPC, 4
- C08K5 28
- C08K5 54
- C08K5 544
- C08L79 04
Designated states8
- Contracting states, 8
- Belgium
- Germany
- Spain
- France
- United Kingdom
- Italy
- Netherlands (Kingdom of the)
- Sweden