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WO2001018136A1 - Matiere de revetement fluoree - Google Patents

Matiere de revetement fluoree 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
Authority
WO
WIPO (PCT)
Prior art keywords
coating solution
solution according
solvent
coating
fluorinated
Prior art date
Application number
PCT/DE2000/002986
Other languages
German (de)
English (en)
Inventor
Gerhard Jonschker
Thomas Benthien
Original Assignee
Nanogate Gmbh
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nanogate Gmbh filed Critical Nanogate Gmbh
Priority to DE10082668T priority Critical patent/DE10082668D2/de
Priority to AU75065/00A priority patent/AU7506500A/en
Publication of WO2001018136A1 publication Critical patent/WO2001018136A1/fr

Links

Classifications

    • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)

Abstract

Solution de revêtement qui contient au moins un fluoroalkylsilane. Selon la présente invention, le solvant est au moins partiellement fluoré, au moins dans une certaine proportion.
PCT/DE2000/002986 1999-09-02 2000-09-01 Matiere de revetement fluoree WO2001018136A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE10082668T DE10082668D2 (de) 1999-09-02 2000-09-01 Fluoriertes Beschichtungsmaterial
AU75065/00A AU7506500A (en) 1999-09-02 2000-09-01 Fluorinated coating material

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1999141752 DE19941752A1 (de) 1999-09-02 1999-09-02 Fluoriertes Beschichtungsmaterial
DE19941752.0 1999-09-02

Publications (1)

Publication Number Publication Date
WO2001018136A1 true WO2001018136A1 (fr) 2001-03-15

Family

ID=7920504

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE2000/002986 WO2001018136A1 (fr) 1999-09-02 2000-09-01 Matiere de revetement fluoree

Country Status (3)

Country Link
AU (1) AU7506500A (fr)
DE (2) DE19941752A1 (fr)
WO (1) WO2001018136A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7087694B2 (en) 2000-11-15 2006-08-08 E. I. Du Pont De Nemours And Company Fluorinated copolymers for hydrophobic and oleophobic treatment of building materials

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005060401A1 (de) * 2005-12-15 2007-06-21 Degussa Gmbh Lagerstabile Beschichtungszusammensetzung für eine abriebfeste und witterungsbeständige Ausstattung glatter anorganischer Oberflächen mit "Easy-to-clean"-Eigenschaften

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0328397A2 (fr) * 1988-02-12 1989-08-16 Shin-Etsu Chemical Co., Ltd. Composés organosilicium contenant du fluor et leur procédé de préparation
US5523161A (en) * 1990-04-03 1996-06-04 Ppg Industries, Inc. Water repellent surface treatment with integrated primer
US5688864A (en) * 1990-04-03 1997-11-18 Ppg Industries, Inc. Autophobic water repellent surface treatment
WO1998051651A1 (fr) * 1997-05-16 1998-11-19 Nippon Zeon Co., Ltd. Hydrocarbures fluores, detergents, procede detergent, fluides a base de polymeres et procede de formation de films polymeres
JPH11116810A (ja) * 1997-10-17 1999-04-27 Shin Etsu Chem Co Ltd 表面処理剤
WO1999037720A1 (fr) * 1998-01-27 1999-07-29 Minnesota Mining And Manufacturing Company Revetements anti-salissures pour surfaces antireflet et procedes de preparation
US6140451A (en) * 1997-10-17 2000-10-31 Shin-Etsu Chemical Co., Ltd. Surface treating compositions

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0328397A2 (fr) * 1988-02-12 1989-08-16 Shin-Etsu Chemical Co., Ltd. Composés organosilicium contenant du fluor et leur procédé de préparation
US5523161A (en) * 1990-04-03 1996-06-04 Ppg Industries, Inc. Water repellent surface treatment with integrated primer
US5688864A (en) * 1990-04-03 1997-11-18 Ppg Industries, Inc. Autophobic water repellent surface treatment
EP0719743A1 (fr) * 1994-12-27 1996-07-03 Ppg Industries, Inc. Traitement de surface hydrofuge avec un revêtement primaire intégré
WO1998051651A1 (fr) * 1997-05-16 1998-11-19 Nippon Zeon Co., Ltd. Hydrocarbures fluores, detergents, procede detergent, fluides a base de polymeres et procede de formation de films polymeres
EP0994089A1 (fr) * 1997-05-16 2000-04-19 Nippon Zeon Co., Ltd. Hydrocarbures fluores, detergents, procede detergent, fluides a base de polymeres et procede de formation de films polymeres
JPH11116810A (ja) * 1997-10-17 1999-04-27 Shin Etsu Chem Co Ltd 表面処理剤
US6140451A (en) * 1997-10-17 2000-10-31 Shin-Etsu Chemical Co., Ltd. Surface treating compositions
WO1999037720A1 (fr) * 1998-01-27 1999-07-29 Minnesota Mining And Manufacturing Company Revetements anti-salissures pour surfaces antireflet et procedes de preparation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 1999, no. 09 30 July 1999 (1999-07-30) *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7087694B2 (en) 2000-11-15 2006-08-08 E. I. Du Pont De Nemours And Company Fluorinated copolymers for hydrophobic and oleophobic treatment of building materials

Also Published As

Publication number Publication date
AU7506500A (en) 2001-04-10
DE19941752A1 (de) 2001-04-12
DE10082668D2 (de) 2002-08-14

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