DE4130077A1 - Coating compsn. for glass fibres - comprising aq. protein soln. e.g. casein contg. hardener e.g. aliphatic aldehyde, for improved resistance to aggressive media e.g. acid - Google Patents

Coating compsn. for glass fibres - comprising aq. protein soln. e.g. casein contg. hardener e.g. aliphatic aldehyde, for improved resistance to aggressive media e.g. acid

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Publication number
DE4130077A1
DE4130077A1 DE4130077A DE4130077A DE4130077A1 DE 4130077 A1 DE4130077 A1 DE 4130077A1 DE 4130077 A DE4130077 A DE 4130077A DE 4130077 A DE4130077 A DE 4130077A DE 4130077 A1 DE4130077 A1 DE 4130077A1
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DE
Germany
Prior art keywords
glass
fibres
casein
protein
hardener
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.)
Withdrawn
Application number
DE4130077A
Other languages
German (de)
Inventor
Klaus Dr Forkel
Dieter Dr Vollhardt
Horst Dr Hermel
Georg Prof Dr Tomaschewski
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ZENTRALINSTITUT fur ORGANISCH
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ZENTRALINSTITUT fur ORGANISCH
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Filing date
Publication date
Application filed by ZENTRALINSTITUT fur ORGANISCH filed Critical ZENTRALINSTITUT fur ORGANISCH
Priority to DE4130077A priority Critical patent/DE4130077A1/en
Publication of DE4130077A1 publication Critical patent/DE4130077A1/en
Withdrawn legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10Coating
    • C03C25/24Coatings containing organic materials
    • C03C25/26Macromolecular compounds or prepolymers
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Textile Engineering (AREA)
  • Surface Treatment Of Glass Fibres Or Filaments (AREA)

Abstract

Coating compsn. comprises aq. soln. with 1-25 wt.% of protein and 1-80%, w.r.t. protein solids content, of hardener. Pref. the protein is casein or gelatin, and the hardener is aliphatic or aromatic aldehyde, cyanuric acid chloride, or chromate ions. USE/ADVANTAGE - The compsn. is used on spun glass silk fibres or fabric, glass fibre mats, stable glass fibres, or mineral wool, for use in the glass, building and synthetics industries. Resistance of the glass fibres to aggressive media, esp. to acids, is improved. In an example, mixt. of 800 g of casein, 76 g of borax 0.2g of "E 20" (RTM: Na alkane sulphonate of medum chain length) and 2120g of water was stirred for 4.5 h. at 50-60 deg.C. The soln. could be used after cooling, or could be kept for weeks after addn. of 6g of phenol. 3 wt.% of propionaldehyde was added to the soln., and fibres or E-glass were coated with the compsn. and dried at 130 deg.C. 20 m of the coated fibres were immersed for 10 weeks at room temp. in 200ml of 2.5% H2SO4. The amt. of Al3+ ions extracted from the fibres was 1.54 mg/ml of H2SO4, compared with 3.15 mg Al/ml H2SO4 for the uncoated

Description

Die Erfindung betrifft ein Mittel zur Beschichtung von Glasfasern, wie Glasseidenspinnfäden, Glasstapelfasern, Glasseidengewebe, Glasfasermatten oder Mineralwolle, wie sie in der Glas-, Baustoff- und Kunststoffindustrie Anwendung finden.The invention relates to an agent for coating glass fibers, such as glass fiber spun threads, glass staple fibers, glass silk fabrics, Glass fiber mats or mineral wool as used in glass, building materials and plastics industry find application.

Glasfasern werden üblicherweise unmittelbar nach dem Ziehen zum Schutz vor mechanischen Beanspruchungen, wie Abrieb oder Bruch, und zur Verbesserung der Gleiteigenschaften sowie der oberflächen­ chemischen Verträglichkeit gegenüber verschiedensten Verbundwerk­ stoffkomponenten mit Überzügen versehen.Glass fibers usually become immediately after pulling Protection against mechanical stress, such as abrasion or breakage and to improve the sliding properties and the surfaces chemical compatibility with various composite structures cover the fabric components.

Gebräuchlich sind hierzu Silanhaftmittel oder Chrom-Methacrylat- Komplexsalze, die sogenannten Chromschlichten, die inform von verdünnten Lösungen in Isopropanol oder wäßrigem Ammoniak ins­ besondere zur Herstellung von Kunststofflaminaten auf der Basis von ungesättigten Polyesterharzen, Epoxidharzen, Phenolharzen und Acrylharzen angewendet werden. Diese Hilfsmittel beeinflussen zwar die unmittelbare Verarbeitbarkeit der Glasfasern, bieten jedoch keinen längerfristigen Schutz der Fasern gegenüber aggressiven Medien.Silane adhesives or chrome methacrylate Complex salts, the so-called chrome coatings, which inform about dilute solutions in isopropanol or aqueous ammonia especially for the production of plastic laminates on the basis of unsaturated polyester resins, epoxy resins, phenolic resins and Acrylic resins can be applied. These tools do influence the immediate processability of the glass fibers, however, offer no long-term protection of the fibers against aggressive Media.

In der Erfindungsschrift SU 5 95 351 wird auch eine Schutzschicht, bestehend aus einem Methacrylatcopolymer, Epoxid-Dian-Harz, Hydro­ chinon und Dimethylanilin, beschrieben, die jedoch die Verwendung von organischen Lösungsmitteln erfordert und somit für den Glas­ seidenspinnprozeß ungeeignet ist.In SU 5 95 351, a protective layer, consisting of a methacrylate copolymer, epoxy dian resin, hydro quinone and dimethylaniline, but described the use of organic solvents and therefore for glass silk spinning process is unsuitable.

Der Erfindung liegt die Aufgabe zugrunde, durch eine neues Mittel zur Beschichtung von Glasfasern, deren Widerstandsfähigkeit gegen­ über aggressiven Medien, insbesondere deren Säurebeständigkeit, zu verbessern. The invention has for its object by a new means for coating glass fibers, their resistance to aggressive media, especially their acid resistance improve.  

Die Aufgabe wird erfindungsgemäß durch ein Mittel gelöst, das aus einer Proteinlösung (Casein, Gelatine) und 1 bis 80 Ma.-%, bezogen auf den Feststoffgehalt des Proteins, eines Härtungsmittels be­ steht. Der Proteingehalt der Lösung beträgt dabei 2 bis 25 Ma.-%.According to the invention, the object is achieved by a means which consists of a protein solution (casein, gelatin) and 1 to 80% by mass on the solids content of the protein, a hardening agent stands. The protein content of the solution is 2 to 25 mass%.

Als Härtungsmittel eignen sich aliphatische Aldehyde (zum Beispiel Form-, Acet-, Propion-, Butyraldehyd) und aromatische Aldehyde wie Benz-, o- und p-Hydroxyanisaldehyd.Aliphatic aldehydes (for example Form, acet, propione, butyraldehyde) and aromatic aldehydes such as Benz-, o- and p-hydroxyanisaldehyde.

Als weitere Härtungsmittel sind Cyanursäurechlorid und Chromat­ ionen liefernde Verbindungen wie Ammoniumdichromat einsetzbar.Cyanuric acid chloride and chromate are further curing agents ion-providing compounds such as ammonium dichromate can be used.

Durch diese erfindungsgemäße Kombination von Proteinen, die bisher zur Beschichtung von anorganischen-nichtmetallischen Fasern keine Anwendung fanden, und Härtungsmitteln wird eine chemische Modifi­ zierung der Proteinkomponente erreicht, die gravierende Eigen­ schaftsänderungen zur Folge hat. Diese gehärteten Proteine bilden auf den Glasfasern festhaftende, mechanischen Beanspruchungen standhaltende Schutzschichten, die sich durch eine hohe chemische Stabilität gegenüber dem Angriff aggressiver chemischer Medien auszeichnen.Through this combination of proteins according to the invention, which so far none for coating inorganic-non-metallic fibers Chemical modifi Decoration of the protein component achieved the grave own changes in society. Form these hardened proteins mechanical loads adhering to the glass fibers resistant protective layers, which are characterized by a high chemical Stability against attack by aggressive chemical media award.

Die Erfindung wird anhand der nachstehenden Beispiele noch näher erläutert.The invention is further illustrated by the examples below explained.

Beispiel 1example 1 Herstellung der CaseingrundlösungProduction of the basic case solution

800 g Casein, 76 g Borax und 0,2 g E 20 (Natrium-Alkansulfonat mittlerer Kohlenstoff-Kettenlänge, Hersteller Leuna-Werke) werden mit 2120 g Wasser gemischt und 4,5 Stunden bei 50 bis 60°C ge­ rührt. Nach dem Abkühlen ist diese Lösung verwendbar und durch die Zugabe von 6,0 g Phenol über Wochen lagerfähig.800 g casein, 76 g borax and 0.2 g E 20 (sodium alkanesulfonate medium carbon chain length, manufacturer Leuna-Werke) mixed with 2120 g of water and ge for 4.5 hours at 50 to 60 ° C. stirs. After cooling, this solution is usable and by the 6.0 g of phenol can be stored for weeks.

  • a) E-Glasseiden-Spinnfäden werden mit dieser Caseingrundlösung (Feststoffgehalt 7,0 Ma.-%) beschichtet und anschließend zwei Stunden bei 130°C getrocknet.a) E-glass silk spun threads with this basic case solution (Solids content 7.0 mass%) coated and then two Dried at 130 ° C for hours.
  • b) 10 Teilen der Caseingrundlösung wird 1 Teil einer 3-%igen Ammoniumdichromat-Lösung zugefügt. Mit dieser Lösung werden dann die E-Glasseiden-Spinnfäden beschichtet und anschließend bei 130°C getrocknet.b) 10 parts of the basic case solution becomes 1 part of a 3% solution Ammonium dichromate solution added. With this solution then coated the E-glass silk filaments and then dried at 130 ° C.
  • c) Der Caseingrundlösung werden unter Rühren 3 Ma.-% Propion­ aldehyd zugegeben. Die E-Glasseiden-Spinnfäden werden mit die­ ser Lösung beschichtet und danach bei 130°C getrocknet.c) The casein basic solution with stirring 3 Ma .-% propion aldehyde added. The E-glass silk spun threads are with the coated water solution and then dried at 130 ° C.

Zur Stabilitätstestung werden jeweils 20 m dieser beschichteten Glasseiden-Spinnfäden für 10 Wochen bei Raumtemperatur der Einwir­ kung von 200 ml 2,5-%iger H2SO4 ausgesetzt und anschließend die aus dem Glas herausgelöste Al3+-Ionenkonzentration atomabsorptionsspek­ troskopisch gemessen.For stability testing, 20 m of these coated glass silk spun threads are exposed for 10 weeks at room temperature to the action of 200 ml of 2.5% H 2 SO 4 and then the Al 3+ ion concentration released from the glass is measured by atomic absorption spectroscopy.

Während aus der unbeschichteten E-Glasfaser unter diesen Bedingun­ gen 3,15 mg Al3+-Ionen/ml 2,5-%iger H2SO4 herausgelöst werden, sind es bei den mit dem gehärteten Casein beschichteten Glasfasern nur noch 1,54 mg Al3+-Ionen/ml 2,5-%iger H2SO4.While 3.15 mg Al 3+ ions / ml 2.5% H 2 SO 4 are dissolved out of the uncoated E-glass fiber under these conditions, it is only 1.54 for the glass fibers coated with the hardened casein mg Al 3+ ions / ml 2.5% H 2 SO 4 .

Beispiel 2Example 2 Herstellung der GelatinegrundlösungPreparation of the gelatin base solution

200 g Gelatine werden in 1500 g Wasser bei Raumtemperatur minde­ stens drei Stunden unter gelegentlichem Umrühren gequollen. An­ schließend wird die Gelatine wiederum unter gelegentlichem Umrüh­ ren bei 40 bis 60°C aufgeschmolzen, so daß eine klare kolloidale Lösung entsteht.200 g of gelatin are mined in 1500 g of water at room temperature swollen for at least three hours, stirring occasionally. On finally the gelatin is again stirred occasionally ren melted at 40 to 60 ° C, so that a clear colloidal Solution arises.

  • a) Dieser Gelatinegrundlösung werden ebenfalls bei 40 bis 60°C 160 g in 500 g Wasser gelöstes Cyanursäurechlorid zugesetzt. Mit dieser, einen Gelatineanteil von 8 Ma.-% aufweisenden Lösung werden E-Glasseiden-Spinnfäden beschichtet und anschlie­ ßend zwei Stunden bei 130°C getrocknet.a) This gelatin base solution are also at 40 to 60 ° C. 160 g of cyanuric acid chloride dissolved in 500 g of water are added. With this, a gelatin content of 8% by mass Solution, E-glass fiber filaments are coated and then dried at 130 ° C for two hours.
  • b) E-Glasseiden-Spinnfäden werden mit der Gelatinegrundlösung be­ schichtet und dann zwei Stunden bei 130°C getrocknet.b) E-glass silk spun threads are loaded with the gelatin base solution layers and then dried for two hours at 130 ° C.

Zur Stabilitätstestung werden jeweils 20 m dieser beschichteten Glasseiden-Spinnfäden für 10 Wochen bei Raumtemperatur der Einwir­ kung von 200 ml 2,5-%iger H2SO4 ausgesetzt und anschließend die aus dem Glas herausgelöste Al3+-Ionenkonzentration atomabsorptionsspek­ troskopisch gemessen.For stability testing, 20 m of these coated glass silk spun threads are exposed for 10 weeks at room temperature to the action of 200 ml of 2.5% H 2 SO 4 and then the Al 3+ ion concentration released from the glass is measured by atomic absorption spectroscopy.

Während aus den mit der Gelatinegrundlösung beschichteten E-Glas­ seiden-Spinnfäden unter diesen Bedingungen 1,67 mg Al3+-Ionen/ml 2,5-%iger H2SO4 herausgelöst werden, sind es bei den mit der ausge­ härteten Gelatine beschichteten Glasfasern nur noch 1,19 mg Al3+-Ionen/ml 2,5-%iger H2SO4.While 1.67 mg Al 3+ ions / ml 2.5% H 2 SO 4 are dissolved out of the E-glass silk filaments coated with the gelatin base solution under these conditions, it is the case with those coated with the hardened gelatin Glass fibers only 1.19 mg Al 3+ ions / ml 2.5% H 2 SO 4 .

Claims (3)

1. Mittel zur Beschichtung von Glasfasern, dadurch gekennzeichnet, daß es aus einer wäßrigen Proteinlösung mit einem Proteingehalt von 1 bis 25 Ma.-% und 1 bis 80 Ma.-%, bezogen auf den Fest­ stoffgehalt des Proteins, eines Härtungsmittels besteht.1. Agent for coating glass fibers, characterized in that it consists of an aqueous protein solution with a protein content of 1 to 25% by mass and 1 to 80% by mass, based on the solids content of the protein, of a hardening agent. 2. Mittel nach Anspruch 1, dadurch gekennzeichnet, daß als Protein Casein oder Gelatine eingesetzt werden.2. Composition according to claim 1, characterized in that as a protein Casein or gelatin can be used. 3. Mittel nach Anspruch 1, dadurch gekennzeichnet, daß das Här­ tungsmittel aliphatische oder aromatische Aldehyde, Cyanur­ säurechlorid oder Chromationen darstellen.3. Means according to claim 1, characterized in that the hardening aliphatic or aromatic aldehydes, cyanur represent acid chloride or chromate ions.
DE4130077A 1991-09-06 1991-09-06 Coating compsn. for glass fibres - comprising aq. protein soln. e.g. casein contg. hardener e.g. aliphatic aldehyde, for improved resistance to aggressive media e.g. acid Withdrawn DE4130077A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE4130077A DE4130077A1 (en) 1991-09-06 1991-09-06 Coating compsn. for glass fibres - comprising aq. protein soln. e.g. casein contg. hardener e.g. aliphatic aldehyde, for improved resistance to aggressive media e.g. acid

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Application Number Priority Date Filing Date Title
DE4130077A DE4130077A1 (en) 1991-09-06 1991-09-06 Coating compsn. for glass fibres - comprising aq. protein soln. e.g. casein contg. hardener e.g. aliphatic aldehyde, for improved resistance to aggressive media e.g. acid

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DE4130077A1 true DE4130077A1 (en) 1993-03-11

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017194722A1 (en) * 2016-05-13 2017-11-16 Rockwool International A/S Mineral wool binder
WO2021032645A1 (en) * 2019-08-16 2021-02-25 Rockwool International A/S Mineral wool binder
RU2775636C2 (en) * 2016-05-13 2022-07-05 Роквул Интернэшнл А/С Binder composition
US11846052B2 (en) 2017-05-11 2023-12-19 Rockwool A/S Method of manufacturing a moulded mineral wool product and a product of such kind

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2776738C2 (en) * 2016-05-13 2022-07-26 Роквул Интернэшнл А/С Composition of the binder
US12070929B2 (en) 2016-05-13 2024-08-27 Rockwool A/S Mineral wool product
WO2017194724A3 (en) * 2016-05-13 2017-12-21 Rockwool International A/S Binder composition for mineral fibers comprising at least one hydrocolloid
WO2017194725A3 (en) * 2016-05-13 2017-12-21 Rockwool International A/S Binder composition for mineral fibers comprising at least one hydrocolloid
CN109562988A (en) * 2016-05-13 2019-04-02 洛科威国际有限公司 Mineral wool binder
US12502879B2 (en) 2016-05-13 2025-12-23 Rockwool A/S Binder composition
US11174578B2 (en) 2016-05-13 2021-11-16 Rockwool International A/S Method of bonding together surfaces of two or more elements and a product made by said method
RU2775636C2 (en) * 2016-05-13 2022-07-05 Роквул Интернэшнл А/С Binder composition
WO2017194720A1 (en) * 2016-05-13 2017-11-16 Rockwool International A/S Coherent composite
US11820116B2 (en) 2016-05-13 2023-11-21 Rockwool A/S Binder composition
US11590747B2 (en) 2016-05-13 2023-02-28 Rockwool International A/S Method of producing a mineral wool product comprising a multiple of lamellae and a product of such kind
US12397537B2 (en) 2016-05-13 2025-08-26 Rockwool A/S Fire-protecting insulation product and use of such product
US11865826B2 (en) 2016-05-13 2024-01-09 Rockwool A/S Method of producing a mineral wool product comprising a multiple of lamellae and a product of such kind
WO2017194722A1 (en) * 2016-05-13 2017-11-16 Rockwool International A/S Mineral wool binder
US12123117B2 (en) 2017-05-11 2024-10-22 Rockwool A/S Binder composition for mineral fibers comprising at least one hydrocolloid and a fatty acid ester of glycerol
US11846052B2 (en) 2017-05-11 2023-12-19 Rockwool A/S Method of manufacturing a moulded mineral wool product and a product of such kind
US12398070B2 (en) 2019-08-16 2025-08-26 Rockwool A/S Mineral wool binder
WO2021032645A1 (en) * 2019-08-16 2021-02-25 Rockwool International A/S Mineral wool binder

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