WO2001018136A1 - Fluorinated coating material - Google Patents

Fluorinated coating material Download PDF

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Publication number
WO2001018136A1
WO2001018136A1 PCT/DE2000/002986 DE0002986W WO0118136A1 WO 2001018136 A1 WO2001018136 A1 WO 2001018136A1 DE 0002986 W DE0002986 W DE 0002986W WO 0118136 A1 WO0118136 A1 WO 0118136A1
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Prior art keywords
coating solution
solution according
solvent
coating
fluorinated
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PCT/DE2000/002986
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German (de)
French (fr)
Inventor
Gerhard Jonschker
Thomas Benthien
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Nanogate Gmbh
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Priority to AU75065/00A priority Critical patent/AU7506500A/en
Priority to DE10082668T priority patent/DE10082668D2/en
Publication of WO2001018136A1 publication Critical patent/WO2001018136A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
    • C08J3/093—Halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen

Definitions

  • the present invention is concerned with the preparation of a fluorinated Besch ⁇ chtungsmate ⁇ als, a fluorinated coating material per se, and in particular with a reflectivity changing the coating.
  • Bescn ⁇ chtungsmate ⁇ al_er are known per se.
  • a known coating is produced on the basis of perfluoroalkylsilanes. This known coating has many properties which are desirable for coatings, such as non-stick properties, etc. It is disadvantageous that the known coatings based on perfluoroalkylsilanes have hitherto only been able to be applied in very thin layer thicknesses to surfaces ( ⁇ 1 - 2 ⁇ m). This further reduces the low abrasion resistance.
  • the known coatings are also not completely uniform, because when a critical layer thickness is exceeded the layer forming drops and tears and runs off. This is done approximately in the same way as the appearance of "tears" on the edge with high-proof ⁇ nn ⁇ c filled glasses. This behavior is known as the marangonia effect. It has to do with the fact that the solvents evaporate out of the layer that forms and in the process, inhomogeneities arise in the film that forms, which leads to a concentration of the fluorosilane component. Since the typical solvents such as alcohols, ethers or water are polar, mass transport takes place to compensate for polarities. The coating that forms can even tear locally or be destroyed or disturbed in some other way.
  • the autophobic fluorine components collect on the surface of the coating.
  • concentrations are high here, but the layer, which actually contains fluorine, can be removed undesirably quickly, for example by rubbing.
  • the present invention aims to provide innovations for commercial use.
  • the fluoroalkylsilanes have a spacer between each fluorine atom and the subsequent Si atom in the molecule, which has at least one spatial dimension of at least two -CH 2 groups.
  • fluorosilane condensates with a high molar mass can also be dissolved.
  • Such fluorosilane condensates with a high molecular weight can be obtained in particular by heating a fluorosilane hydrolyzate to temperatures up to over 300 ° C .; Even these fluorosilane condensates are still dissolved by the at least partially fluorinated solvents.
  • fluoroalkylsilane condensate dissolved in the at least partially fluorinated solvent, but also in the desired amount of non-fluorinated silane and / or reactive fluoromonomers.
  • non-fluorinated silanes in amounts of, for example, up to 99 percent by weight has the advantage that there is a very high resistance to rubbing of a thick layer, which could not be produced due to the remaining fluoroalkylsilane content in the prior art with a thickness which can be achieved here. It was recognized that when using a partially fluorinated solvent, even with very thick coatings, the flow disturbances known from other solvents are completely eliminated and a nomogenic, uniform film can be obtained, which in particular has a high optical quality.
  • the coatings obtained are particularly suitable as anti-adhesive materials which can be applied at room temperature and nevertheless adhere very well.
  • the above-described disadvantage of known fluorosilane hydrolyzates, according to which the crosslinking is poor and only very incomplete due to steric hindrance and therefore there are still many free silanol groups which impair the non-stick properties, is also overcome.
  • Fluoralkylsilanbe- stratification as erae s ⁇ nst eg obtained only by annealing at 300 ° C .. could.
  • Another advantage of the coatings obtained with a high thickness is the very low refractive index of condensates made from fluoroalkylsilanes compared to glass or common transparent polymers. If the layer thickness is sufficiently high, an anti-reflection effect can also be achieved by means of a coating according to the invention, as can typically only be achieved by multilayer structures with extremely precise layer thicknesses.
  • the material is applied as a single layer and the thickness of the coating is at least largely insignificant in order to achieve the antireflection effect
  • a fully fluorinated solvent can be used as the solvent for the present invention, e.g. C ⁇ F ⁇ or higher homologues. It should also be estimated that fluorine-chlorine-substituted structures, for example Frigene, can be used as the solvent for the present invention.
  • Esters and ketones can also be used as solvents.
  • hydrofluoroethers have been preserved in a practical exemplary embodiment. Excellent results have been achieved in particular with nonafluorobutyl methyl ether and nonafluorobutyl ethyl ether.
  • the solvents can be mixed in any mixing ratio with the fluoroalkylsilanes forming the actual coating. This is possibly very important because the absence of a mixture prevents that after partial evaporation or partial volatilization of the solvent during the coating, the film that forms is torn because the fluoroalkylsilanes do not get into the coating evenly enough. Solvents without mixture gaps are therefore preferred per se.
  • the hydrofluoroether still other solvents such as. 3.
  • Alcohols, ether alcohols, acetone and others can be added without the condensate falling out again.
  • the proportion of the completely or partially fluorinated solution medium in the total surface fraction in a coating solution can therefore be 100 5 -, but can also be less.
  • at least 20% of the partially or completely fluorinated solvent is typically used, and particularly preferably at least 50%.
  • the coating according to the invention with inorganic fillers, for example by mixing in pyrogenic silica in the solution, organosilica sols which are dispersed in alcohols, in particular isopropanol or ethanol, aluminum oxides, in particular in the form of benzene, which are obtained by applying Shear forces are incorporated into the coating solutions; alternatively, other inorganic fillers can be provided.
  • the inorganic fillers increase the hardness of the coating and its abrasion resistance.
  • the inorganic filler content can further contribute to reducing the water vapor diffusion through the coating, which offers advantages in particular when the coating is used for anti-corrosion coatings.
  • the coating composition it is possible to use and / or add fluorinated polymers and / or partially fluorinated polymers, in particular fluorinated fluoralkylacrylates, which can be used in a quantity by weight of up to 99% and in particular improve the mechanical properties and the coating has a very high flexibility, ie to give it flexibility.
  • fluorinated polymers and / or partially fluorinated polymers in particular fluorinated fluoralkylacrylates
  • Silicon-modified, fluorinated or partially fluorinated fluoropolymers can also be used, albeit also in a range of up to 99 percent by weight.
  • the silicon modification of these polymers which are also to be dissolved in the solvent, improves the resistance of the coating by means of compounds between the S lanrest of the polymers and the fluoroalkylsilane condensate.
  • reaction mixture After a reaction time of 2 hours, the reaction mixture is heated to 60 ° C. and water is added while stirring until phase separation occurs. After cooling, the reaction mixture is mixed with a further 500 g of water in a separating funnel and left to stand until the two phases have completely separated from one another.
  • the lower phase is separated and stirred in a three-necked flask in an oil bath with a connected water separator at 260 ° C for 30 minutes.
  • This coating solution can now for applying an anti-adhesive layer can be used to near z ⁇ any substrates.
  • a glass plate pre-cleaned with isopropanol is flooded with the coating material on the oath side and dried at room temperature for 1 hour.
  • the result is an oil and water-repellent protective layer that gives the glass an anti-reflective behavior compared to an uncoated area.
  • Example 2
  • the coating solution is applied to a contacted circuit board.
  • fluoropolymers with hydrophilic groups which are empolyzed to impart water solubility overall, but which lead to massive corrosion problems precisely in the area of printed circuit board manufacture, a considerably improved applicability is achieved in this area according to the invention.
  • the improved corrosion resistance according to the invention is not yet fully understood, but it is believed that the reason for this is the presence of reactive SiO-H groups in the coating, which react with metal oxide groups on the metal surface and thus provide protection against corrosion.
  • Glass plates with different amounts of coating solution per surface are treated.
  • the pretreatment of the glass plate and the coating solution are as described in Example 1.
  • the resulting layer thickness is determined for different amounts of coating solution that have been applied. It was found that layer thicknesses of 50 nm, 100 nm, 400 nm, 800 nm and 4 ⁇ m can be produced without problems.

Abstract

The invention relates to a coating solution that contains at least one fluoroalkylsilane. The solvent used according to the invention is at least partially fluorinated to at least some degree.

Description

Titel Fluoriertes beschichtungsmaterialTitle fluorinated coating material
BescnreibungBescnreibung
Die vorliegende Erfindung befaßt sich mit der Herstellung eines fluorierten Besch^chtungsmateπals, einem fluorierten Beschichtungsmaterial an sich, sowie insbesondere mit einer die Reflektivitat verändernden Beschichtung.The present invention is concerned with the preparation of a fluorinated Besch ^ chtungsmateπals, a fluorinated coating material per se, and in particular with a reflectivity changing the coating.
Bescnιchtungsmateπal_er an sich sind bekannt. Eine bekannte Beschichtung wirα a f Basis von Perfluoralkylsilanen hergestellt. Diese bekannte Beschichtung hat viele für Beschich- tugnen wünschenswerte Eigenschaften, wie Antihafteigenschaf- ten usw.. Nachteilig ist, daß die bekannten Beschichtungen auf Basis von Perfluoralkylsilanen bislang nur in sehr dünnen Schichtdicken auf Ooerflachen aufgebracht werden (< 1 - 2 μm) können. Dies verringert die ohnenin geringe Abriebsfestigkeit weiter.Bescnιchtungsmateπal_er are known per se. A known coating is produced on the basis of perfluoroalkylsilanes. This known coating has many properties which are desirable for coatings, such as non-stick properties, etc. It is disadvantageous that the known coatings based on perfluoroalkylsilanes have hitherto only been able to be applied in very thin layer thicknesses to surfaces (<1 - 2 μm). This further reduces the low abrasion resistance.
Ursächlich hierfür ist vermutlich ein Autophobie-Effekt, der bewirkt, daß die sich oildende Beschichtung weiteres Beschichtungsmaterial abstoßt, welches andernfalls in die Beschichtung eingebaut werαer konnte.The reason for this is presumably an autophobia effect, which causes the coating which forms to repel further coating material which could otherwise have been incorporated into the coating.
Zudem sind die Gekannten Beschichtungen auch nicht völlig gleichmäßig aαfzαtraαen, denn beim Überschreiten einer kritischen Schichtdicke
Figure imgf000002_0001
die S ch bildende Schicht zu Tropfen bzw. Tranen zusammen und lauft ab. Dies erfolgt etwa in der gleichen Weise wie da Auftreten von „Tranen" am Rande mit hochprozentigem Ξ nn^c gefüllter Glasern. Dieses Verhalten ist als Marangonie - Effekt bekannt. Es hangt damit zusammen, daß die Losungsmittel aus der sich bildenden Schicht heraus verdampfen und dabei im sich bildenden Film Inhomogenitäten entstehen, die zu einer Aufkonzentration der Fluorsilankomponente fuhrt. Da die typischen Losungsmittel wie Alkohole, Etner oder auch Wasser polar sind, findet dann ein Massentransport zum Ausgleich von Polaritäten statt. Dabei kann die sich bildende Beschichtung sogar lokal reißen oder auf andere Weise zerstört bzw. gestört werden.In addition, the known coatings are also not completely uniform, because when a critical layer thickness is exceeded
Figure imgf000002_0001
the layer forming drops and tears and runs off. This is done approximately in the same way as the appearance of "tears" on the edge with high-proof Ξ nn ^ c filled glasses. This behavior is known as the marangonia effect. It has to do with the fact that the solvents evaporate out of the layer that forms and in the process, inhomogeneities arise in the film that forms, which leads to a concentration of the fluorosilane component. Since the typical solvents such as alcohols, ethers or water are polar, mass transport takes place to compensate for polarities. The coating that forms can even tear locally or be destroyed or disturbed in some other way.
Es ist damit im Stand der Technik praktisch unmöglich, Beschichtungen mit Fl jorsxlanKomponenten zu erzeugen, die eine bestimmte Dicke überschreiten.It is therefore practically impossible in the prior art to produce coatings with fluoroslan components that exceed a certain thickness.
Die Beschichtungen mit Fluoralkylsilanen im Stand der Technik weisen aber weitere Nachteile auf. So wird m der Regel durch sterische Behinderung der Fluoralkylsilane eine nur schlechte Vernetzung erzielt; bisher Dekannte Fluorsilanhydrolysate, die bei Raumtemperatur auf Oderflachen aufgebracht werden, vernetzen nur sehr unvollständig und können daher noch viele freie Silanolgruppen enthalten, was die Antihafteigenschaften verschlechtern .However, the coatings with fluoroalkylsilanes in the prior art have further disadvantages. Thus, as a rule, only poor crosslinking is achieved through steric hindrance of the fluoroalkylsilanes; Previously known fluorosilane hydrolyzates, which are applied to Oder surfaces at room temperature, only crosslink very incompletely and can therefore still contain many free silanol groups, which worsens the non-stick properties.
Zudem sammeln sich die autophoben Fluorkomponenten an der Oberflache der Beschichtung. Hier sind zwar die Konzentrationen hoch, aber die tatsachlich fluorhaltige Schicht kann unerwünscht schnell etwa durch Reiben abgetragen werden.In addition, the autophobic fluorine components collect on the surface of the coating. The concentrations are high here, but the layer, which actually contains fluorine, can be removed undesirably quickly, for example by rubbing.
Außerdem erfolgt unter einigen der bekannten Beschichtungen mit fluorierten Polymeren oftmals eine Korrosion des beschichteten Materials. Dies ist insbesondere bei Leiterplatten gravierend. Die vorliegende Erfindung zielt darauf, Neues für die gewerbliche Anwendung bereitzustellen.In addition, some of the known fluorinated polymer coatings often corrode the coated material. This is particularly serious with printed circuit boards. The present invention aims to provide innovations for commercial use.
Dieses Ziel wird erreicht unter Zugrundelegung der uberra- sehenden Beobachtung, daß Kondensate aus Fluoralkylsilanen, selbst ohne jegliche Stabilisierung durch weitere organische oder anorganische Moleküle oder Ionen, in einem mindestens teilfluorierten Losunσs ittel gelost und dann sehr homogen, gleichmäßig und vor allem dick auf praktisch beliebige Ober- flachen aufgebracht werden können. Die Fluoralkylsilane weisen einen Spacer zwischen jedem Fluoratom und dem nachstlie- genden Si-Atom im Molek l auf, welcher wenigstens eine raum- licne Ausdennung von zumindest zwei -CH2~Gruppen besitzt.This goal is achieved on the basis of the surprising observation that condensates from fluoroalkylsilanes, even without any stabilization by further organic or inorganic molecules or ions, are dissolved in an at least partially fluorinated solvent and then very homogeneously, uniformly and above all thickly to practically any Surfaces can be applied. The fluoroalkylsilanes have a spacer between each fluorine atom and the subsequent Si atom in the molecule, which has at least one spatial dimension of at least two -CH 2 groups.
Insbesondere war es überraschend, daß auch Fluorsilankonden- sate mit hoher Molmasse aufgelost werden können. Solche Flu- orsilanenkondensate mit hoher Molmasse können insbesondere durch Erhitzen eines Fluorosilanhydrolysats auf Temperaturen bis über 300 ° C erhalten werden; sogar diese Fluorsilankon- densate werden also noch durch die mindestens teilfluorierten Lösungsmittel aufgelost.In particular, it was surprising that fluorosilane condensates with a high molar mass can also be dissolved. Such fluorosilane condensates with a high molecular weight can be obtained in particular by heating a fluorosilane hydrolyzate to temperatures up to over 300 ° C .; Even these fluorosilane condensates are still dissolved by the at least partially fluorinated solvents.
In einer besonders bevorzugten Variante wird nicht nur Flu- oralkylsilankondensat im mindestens teilfluorierten Losungs- mittel gelost, sondern auch m gewünschter Menge nicht fluoriertes Silan und/oder reaktive Fluormonomere . Die Verwendung von nichtfluorierten Silanen auch in Mengen von beispielsweise bis zu 99 Gewichtsprozent hat den Vorteil, daß sich eine sehr hohe Aoriebsfestigkeit einer dicken Schicht ergibt, wie sie aufgrund des restlichen Fluoralkylsilange- halts im Stand der Tecnnik m hier realisierbarer Dicke nicht herzustellen war. Es wurde erkannt, daß bei Verwendung eines teilfluorierten Losungsmittels auch bei sehr dicken Beschichtungen die von anderen Losungsmitteln her bekannten Verlaufsstorungen völlig unterbleiben und ein nomogener gleichmäßiger Film erhalten werden kann, der insbesondere eine hohe optische Qualität besitzt .In a particularly preferred variant, not only is fluoroalkylsilane condensate dissolved in the at least partially fluorinated solvent, but also in the desired amount of non-fluorinated silane and / or reactive fluoromonomers. The use of non-fluorinated silanes in amounts of, for example, up to 99 percent by weight has the advantage that there is a very high resistance to rubbing of a thick layer, which could not be produced due to the remaining fluoroalkylsilane content in the prior art with a thickness which can be achieved here. It was recognized that when using a partially fluorinated solvent, even with very thick coatings, the flow disturbances known from other solvents are completely eliminated and a nomogenic, uniform film can be obtained, which in particular has a high optical quality.
Werden diese Losungen auf beliebigen Oberflachen aufgetragen, so verdampft das teil luorierte Losungsmittel und es bleibt ein Fluoralkylsilankondensat zurück; dieses hat ausgezeichnete Antihafteigenschaften .If these solutions are applied to any surface, the partially luured solvent evaporates and a fluoroalkylsilane condensate remains; this has excellent non-stick properties.
Man kann also eine beschichtung bei Raumtemperatur auftragen, die praktisch die gleiche Struktur aufweist wie eine bei 300 ° C getemperte Beschichtung, indem man den thermischen Verdichtungsschritt quasi vorwegnimmt und das erhaltene Material m dem speziellen Losungsmittel auflost.It is therefore possible to apply a coating at room temperature which has practically the same structure as a coating which has been tempered at 300 ° C. by virtually anticipating the thermal compression step and dissolving the material obtained in the special solvent.
Die erhaltenen Beschichtungen sind besonders geeignet als An- tihaftmaterialien, die bei Raumtemperatur aufgetragen werden können und dennoch senr gut haften. Der einleitend beschriebene Nachteil bekannter Fluorsilanhydrolysate, wonach durch sterische Behinderung die Vernetzung schlecht und nur sehr unvollständig ist und daher noch viele, die Antihafteigen- schaffen verschlechternde freie Silanolgruppen vorliegen, wird also gleichfalls überwunden.The coatings obtained are particularly suitable as anti-adhesive materials which can be applied at room temperature and nevertheless adhere very well. The above-described disadvantage of known fluorosilane hydrolyzates, according to which the crosslinking is poor and only very incomplete due to steric hindrance and therefore there are still many free silanol groups which impair the non-stick properties, is also overcome.
Zudem erhalt man durch das beschriebene Verfahren selbst auf temperaturempfindlichen Substraten eine Fluoralkylsilanbe- Schichtung, wie sie s^nst z.B. nur durch Tempern bei über 300 °C erhalten erae.. konnte. Es sei jedoch darauf Hingewiesen, daß es ohne weiteres möglich ist, die mit den erfmdαngsgemaßen Beschichtungsmaterial erhaltenen Beschichtungen einem Temperschritt durch Erwärmung des gesamten Substrates und/oder durch oberflächliche Ein- Strahlung von Energie zu unterwerfen. Dies hat eine weitere Erhöhung der Abriebsfestigkeit zur Folge.In addition, one obtains by the described method even on temperature-sensitive substrates, Fluoralkylsilanbe- stratification as erae s ^ nst eg obtained only by annealing at 300 ° C .. could. However, it should be pointed out that it is readily possible to subject the coatings obtained with the coating material according to the invention to a tempering step by heating the entire substrate and / or by superficial radiation of energy. This results in a further increase in abrasion resistance.
Ein weiterer Vorteil αer erhaltenen Beschichtungen mit hoher Dicke ist der im Vergleich zu Glas oder gangigen transparen- ten Polymeren sehr niedrige Brechungsindex von Kondensaten aus Fluoralkylsilanen. Bei ausreichend hoher Schichtdicke kann somit durch eine erfmdungsgemaße Beschichtung auch ein Antireflexeffekt erzielt werden, wie er ansonsten typisch nur durcn Multilayerstrukturen mit extrem präzise einzuhaltenden Schichtdicken erreicπt werden kann.Another advantage of the coatings obtained with a high thickness is the very low refractive index of condensates made from fluoroalkylsilanes compared to glass or common transparent polymers. If the layer thickness is sufficiently high, an anti-reflection effect can also be achieved by means of a coating according to the invention, as can typically only be achieved by multilayer structures with extremely precise layer thicknesses.
Bei der Beschichtung zur Erzielung eines Antireflexeffektes ist besonders gunstig, daß das Material als eine einzige Schicht aufgetragen wird, und die Dicke der Beschichtung zur Erzielung der Antiref exwirkung zumindest weitgehend unerheb¬In the case of the coating to achieve an antireflection effect, it is particularly advantageous that the material is applied as a single layer and the thickness of the coating is at least largely insignificant in order to achieve the antireflection effect
Es ist einzuschätzen, daß eine solche Beschichtung insbesondere bei Solaranlagen eine sinnvolle Anwendung findet. Hier kann einerseits eine Effizienzsteigerung der Solaranlage durch Veπngerung αer Ref exionsverluste schützender Abdek- kungen erhalten werden, andererseits können durch den Anti- hafteffekt Verschmutzungen der Abdeckung oder von Reflektoren vermieden werden, *as gle_cnfalls zu einer deutlichen Steige- rung des Wirkungsgrades beitragt. Dies gilt insbesondere dort, wo Licht gebändelt werden soll, aber durch Staubentwicklung in der Umgeoanα die Reflektoren schnell verschmutzen. Ein typisches
Figure imgf000006_0001
nierfur sind großflächige Sonnen- kraftwerke in ariden und Wustengebieten, aber auch bei herkömmlichen häuslichen Solar- und Photovoltaikfassadenanlagen können sich positive Effekte ergeben.It has to be estimated that such a coating is particularly useful in solar systems. Here, on the one hand, an increase in efficiency of the solar system can be obtained by reducing the reflection losses of protective covers; on the other hand, the non-stick effect can prevent contamination of the cover or of reflectors, * as also contributes to a significant increase in efficiency. This is particularly true where light is to be focused, but quickly pollute the reflectors due to dust in the Umgeoanα. A typical one
Figure imgf000006_0001
nierfur are large-area solar Power plants in arid and desert areas, but also with conventional domestic solar and photovoltaic facade systems can have positive effects.
Es ist einzuschätzen, daß als Losungsmittel für die vorliegende Erfindung ein vollfluoriertes Losungsmittel Verwendung finden kann, z.B. C^Fς oder höhere Homologe. Weiter ist einzuschätzen, daß als Losungsmittel f r die vorliegende Erfindung Fluor-Chlorsubstituierte Strukturen einsetzbar sind, et- wa Frigene.It is appreciated that a fully fluorinated solvent can be used as the solvent for the present invention, e.g. C ^ Fς or higher homologues. It should also be estimated that fluorine-chlorine-substituted structures, for example Frigene, can be used as the solvent for the present invention.
Gleichfalls können Ester und Ketone als Losungsmittel Verwendung finden. So haben sich in einem praktischen Ausfuhrungsbeispiel Hydrofluorether bewahrt. Insbesondere mit Nonafluor- butylmetylether und Nonafluorbutylethylether wurden hervorragende Ergebnisse erzielt. Hier ist auffällig, daß praktisch keine Mischungslucke besteht, d.h. die Losungsmittel sind in jedem beliebigen Mischungsverhaltnisse mit den die eigentliche Beschichtung bildenden Fluoralkylsilanen mischbar. Dies ist womöglich desnalb wichtig, weil die Mischungsluckenfrei- heit verhindert, daß nach partiellem Abdampfen oder partieller Verflüchtigung des Lösungsmittels wahrend der Beschichtung der sich bildende Film etwa deswegen reißt, weil die Fluoralkylsilanen nicht gleichmäßig genug in die Beschichtung gelangen. Lösungsmittel ohne Mischungslucke sind daher per se bevorzugt .Esters and ketones can also be used as solvents. Thus, hydrofluoroethers have been preserved in a practical exemplary embodiment. Excellent results have been achieved in particular with nonafluorobutyl methyl ether and nonafluorobutyl ethyl ether. It is striking here that there is practically no miscibility gap, i.e. the solvents can be mixed in any mixing ratio with the fluoroalkylsilanes forming the actual coating. This is possibly very important because the absence of a mixture prevents that after partial evaporation or partial volatilization of the solvent during the coating, the film that forms is torn because the fluoroalkylsilanes do not get into the coating evenly enough. Solvents without mixture gaps are therefore preferred per se.
Es konnte weiter beobachtet werden, daß nach dem Auflosen des Fluoralkylsilankondensats m dem Hydrofluorether noch weitere Losungsmittel wie z. 3. Alkohole, Etheralkohole, Aceton u.a. zugegeben werden können, ohne daß das Kondensat noch einmal ausfallt. Der Anteil des ganz oder teilfluorierten Losungsmitteis am Gesamtfluiαanteil in einer Beschichtungslosung kann demnach zwar 1005- betragen, aber auch darunter liegen. Um die Nachteile des Standes der Technik zu vermeiden, werden aber typisch zumindest 20% des ganz oder teilfluorierten Losungsmittels eingesetzt und insbesondere bevorzugt wenigstens 50%.It could also be observed that after dissolving the fluoroalkylsilane condensate m the hydrofluoroether still other solvents such as. 3. Alcohols, ether alcohols, acetone and others can be added without the condensate falling out again. The proportion of the completely or partially fluorinated solution medium in the total surface fraction in a coating solution can therefore be 100 5 -, but can also be less. In order to avoid the disadvantages of the prior art, however, at least 20% of the partially or completely fluorinated solvent is typically used, and particularly preferably at least 50%.
Es ist möglich, die erfmdαngsgemaße Beschichtung mit anorganischen Füllstoffen zu versehen, beispielsweise durch das Einmischen pyrogener kieselsauren m die Losung, Organo- Kieselsolen, die in AiKoholen, insbesondere Isopropanol oder Ethanol dispergiert smo, Aluminiumoxiden, insbesondere in Form von Boenmit, die durch Aufbringen von Scherkräften in die Beschichtungslosungen eingearbeitet sind; alternativ können andere anorganische Füllstoffe vorgesehen werden. Die an- organiscnen Füllstoffe erhohen die Harte der Beschichtung und deren Abriebsfestigkeit. Der anorganische Füllstoffanteil kann weiter dazu beitragen, d e Wasserdampfdiffusion durch die Beschichtung zu verringern, was insbesondere beim Einsatz der Beschichtung für korrosionsschutzende Beschichtungen Vor- teile bietet.It is possible to provide the coating according to the invention with inorganic fillers, for example by mixing in pyrogenic silica in the solution, organosilica sols which are dispersed in alcohols, in particular isopropanol or ethanol, aluminum oxides, in particular in the form of benzene, which are obtained by applying Shear forces are incorporated into the coating solutions; alternatively, other inorganic fillers can be provided. The inorganic fillers increase the hardness of the coating and its abrasion resistance. The inorganic filler content can further contribute to reducing the water vapor diffusion through the coating, which offers advantages in particular when the coating is used for anti-corrosion coatings.
In einer bevorzugten ∑iusf hrungsform des Beschichtungsmittels ist es möglich, fluorierte Polymere und/oder teilfluorierte Polymere einzusetzen uno/oder beizumischen, insbesondere flu- orierte Fluralkylacr late, die m einer Gewichtsmenge von bis zu 99 % einsetzbar sind und hierbei insbesondere die mechanischen Eigenschaften veroessern und der Beschichtung eine sehr hohe Flexibilität, d.h. Biegbarkeit zu verleihen. Weiter sind siliziummodifizierte, fluorierte oder teilfluorierte Fluorpo- lymere einsetzbar, αrα zwar gleichfalls in einem Bereich von bis zu 99 Gewichtsprozent. Die Siliziummodifikation dieser gleichfalls im Lösungsmittel aufzulosenden Polymere verbessert die Beständigkeit der Beschichtung, indem Verbindungen zwischen dem S lanrest der Polymere und dem Fluoralkylsilankondensat ermöglicht werden.In a preferred embodiment of the coating composition, it is possible to use and / or add fluorinated polymers and / or partially fluorinated polymers, in particular fluorinated fluoralkylacrylates, which can be used in a quantity by weight of up to 99% and in particular improve the mechanical properties and the coating has a very high flexibility, ie to give it flexibility. Silicon-modified, fluorinated or partially fluorinated fluoropolymers can also be used, albeit also in a range of up to 99 percent by weight. The silicon modification of these polymers, which are also to be dissolved in the solvent, improves the resistance of the coating by means of compounds between the S lanrest of the polymers and the fluoroalkylsilane condensate.
Die Erfindung wird im folgenden nur beispielhaft beschriebenThe invention is described below by way of example only
Beispiel 1:Example 1:
510g von 1H, 1H, 2H, 2H-Trιdekafluoroctyltriethoxysilan werden in 200 ml Isopropanol gelost und anschließend werden 50g IN Salzsaure unter intensiven Ruhren zugetropft.510 g of 1H, 1H, 2H, 2H-trιdekafluoroctyltriethoxysilane are dissolved in 200 ml of isopropanol and then 50 g IN hydrochloric acid are added dropwise with intensive stirring.
Nach 2 Stunden Reaktionszeit wird das Reaktionsgemisch auf 60°C erw rmt und es wird unter R hren Wasser zugetrcpft, bis eine Phasentrennung auftritt. Nach dem Abkühlen wird das Reaktionsgemisch in einem Scheidetrichter mit weiteren 500 g Wasser versetzt und nacn kraftigen Schuttein stehen lassen, bis sich die beiden Phasen komplett voneinander separiert haben.After a reaction time of 2 hours, the reaction mixture is heated to 60 ° C. and water is added while stirring until phase separation occurs. After cooling, the reaction mixture is mixed with a further 500 g of water in a separating funnel and left to stand until the two phases have completely separated from one another.
Die untere Phase w._rd abgetrennt und in einem Dreihaiskolben im Ölbad mit angeschlossenem Wasserabscheider 30 Minuten bei 260 ° C gerührt.The lower phase is separated and stirred in a three-necked flask in an oil bath with a connected water separator at 260 ° C for 30 minutes.
Es resultiert ein glasKlares, bei Raumtemperatur zähflüssiges Harz, welches dann in 5 kg Nonafluorbutylethylether aufgenom- men wird.The result is a crystal-clear, viscous resin at room temperature, which is then taken up in 5 kg of nonafluorobutyl ethyl ether.
Diese Beschichtungslosung kann nun zum Aufbringen einer Anti- haftschicht auf nahe z^ beliebigen Substraten genutzt werden. Eine mit Isopropanol vorgereinigte Glasplatte wird mit dem Beschichtungsmaterial oeidseitig geflutet und bei Raumtemperatur 1 Stunde getrocknet. Es resultiert eine ol- und wasserabweisende Schutzschicht, die dem Glas verglichen mit einer unbeschichteten Stelle ein Antireflexverhalten verleiht. Beispiel 2:This coating solution can now for applying an anti-adhesive layer can be used to near z ^ any substrates. A glass plate pre-cleaned with isopropanol is flooded with the coating material on the oath side and dried at room temperature for 1 hour. The result is an oil and water-repellent protective layer that gives the glass an anti-reflective behavior compared to an uncoated area. Example 2:
Die Beschichtungslosung wird auf eine kontaktierte Leiterplatte aufgeoracht. Es ergibt sich danach auch langfristig keine Kontaktkorrosion. Anders als bei bekannten Fluorpolymeren mit hydrophilen Gruppen, die empolymeπsiert sind, um insgesamt eine Wasserloslichkeit zu vermitteln, aber gerade im Bereich der Leiterplattenherstellung zu massiven Korrosi- onsproblemen fuhren, wird also erfindungsgemaß in diesem Be- reich eine wesentlich verbesserte Emsetzbarkeit erzielt. Die erfindungsgemaß verbesserte Korrosionsbeständigkeit ist noch nicht vollständig verstanden, es wird jedoch angenommen, daß ursächlich hierfür oas Vorhandensein reaktiver SiO-H-Gruppen in der Beschichtung ist, welche mit Metalloxidgruppen auf der Metalloberflache reagieren und somit den Korrosionschutz bewirken .The coating solution is applied to a contacted circuit board. There is no long-term contact corrosion. In contrast to known fluoropolymers with hydrophilic groups, which are empolyzed to impart water solubility overall, but which lead to massive corrosion problems precisely in the area of printed circuit board manufacture, a considerably improved applicability is achieved in this area according to the invention. The improved corrosion resistance according to the invention is not yet fully understood, but it is believed that the reason for this is the presence of reactive SiO-H groups in the coating, which react with metal oxide groups on the metal surface and thus provide protection against corrosion.
Beispiel 3:Example 3:
Es werden Glasplatter mit unterschiedlichen Mengen an Be- schichtungslosung pro Flache behandelt. Die Vorbehandlung der Glasplatte und die Beschichtungslosung sind wie in Beispiel 1 beschrieben. Die resultierende Schichtdicke wird für verschiedene Mengen an Beschichtungslosung, die aufgetragen wurden bestimmt. Es wurde festgestellt, daß sich Schichtdicken von 50 nm, 100 nm, 400 nm, 800 nm sowie von 4 μm problemfrei herstellen lassen. Glass plates with different amounts of coating solution per surface are treated. The pretreatment of the glass plate and the coating solution are as described in Example 1. The resulting layer thickness is determined for different amounts of coating solution that have been applied. It was found that layer thicknesses of 50 nm, 100 nm, 400 nm, 800 nm and 4 μm can be produced without problems.

Claims

Patentansprüche claims
1. Beschichtungslosung mit wenigstens einem Fluoralkylsilan, dadurch gekennzeichnet, daß das Losungsmuttel mindestens anteilsweise mindestens teilfluoriert ist.1. coating solution with at least one fluoroalkylsilane, characterized in that the solvent is at least partially at least partially fluorinated.
2. Beschichtungslosung nach dem vorhergehenden Anspruch, dadurch gekennzeichnet, daß die Fluoralkylsilane als Kon- densate vorliegen.2. Coating solution according to the preceding claim, characterized in that the fluoroalkylsilanes are present as condensates.
3. Beschichtungslosung nach dem vorhergehenden Anspruch, dadurch gekennzeichnet, daß die Fluorsilankondensatmolmasse mindestens großer tausend Gramm pro mol ist.3. Coating solution according to the preceding claim, characterized in that the fluorosilane condensate mol mass is at least a large thousand grams per mol.
Beschichtungslosung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das Losungsmittel zumindest teilweise aus einer vollfluorierten Verbindung besteht, insbesondere C∑Fς oder höhere Homologe.Coating solution according to one of the preceding claims, characterized in that the solvent consists at least partially of a fully fluorinated compound, in particular C ∑ Fς or higher homologues.
Beschichtungslosung nacn einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das Losungsmittel Fluor- Chlorsubstituierte Strukturen umfaßt.Coating solution according to one of the preceding claims, characterized in that the solvent comprises fluorine-chlorine-substituted structures.
6. Beschichtungslosung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das Losungsmittel aus Hydrofluorether , lnsoesondere Nonafluorbutylmetylether und/oder Nonafluorbutylethylether ausgewählt ist und/oder zumindest eine dieser Suostanzen umfaßt.6. Coating solution according to one of the preceding claims, characterized in that the solvent is selected from hydrofluoroether, inso special nonafluorobutyl methyl ether and / or nonafluorobutyl ethyl ether and / or comprises at least one of these suostances.
Beschichtungslosung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß der Anteil des oder der 8136Coating solution according to one of the preceding claims, characterized in that the proportion of the or 8136
ganz und/oder teilfluorierten Losungsmittel mindestens 20% beträgt.whole and / or partially fluorinated solvent is at least 20%.
8. Beschichtungslosung nach einem der vorhergehenden Ansprü- ehe, dadurch gekennzeichnet, daß weiter Fluorpolymere, insbesondere Polymerisate aus Fluoralkylacrylaten in dem teilfluorierten Losungsmittel gelöst sind.8. Coating solution according to one of the preceding claims, characterized in that further fluoropolymers, in particular polymers of fluoroalkyl acrylates, are dissolved in the partially fluorinated solvent.
9. Beschichtungslosung nach dem vorhergehenden Anspruch, da- durch gekennzeichnet, daß der Anteil an fluorierten und/oder teilfluorierten Polymerisaten zwischen 0 und 99 Gewichtsprozent betragt. 9. Coating solution according to the preceding claim, characterized in that the proportion of fluorinated and / or partially fluorinated polymers is between 0 and 99 percent by weight.
PCT/DE2000/002986 1999-09-02 2000-09-01 Fluorinated coating material WO2001018136A1 (en)

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