EP1363979A1 - Procede de preparation de condensats sol-gel a base d'organosilanes a fonctions multiples, et leur utilisation - Google Patents

Procede de preparation de condensats sol-gel a base d'organosilanes a fonctions multiples, et leur utilisation

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Publication number
EP1363979A1
EP1363979A1 EP02702272A EP02702272A EP1363979A1 EP 1363979 A1 EP1363979 A1 EP 1363979A1 EP 02702272 A EP02702272 A EP 02702272A EP 02702272 A EP02702272 A EP 02702272A EP 1363979 A1 EP1363979 A1 EP 1363979A1
Authority
EP
European Patent Office
Prior art keywords
sol
gel
polyfunctional
spoke
condensate
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Withdrawn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
EP02702272A
Other languages
German (de)
English (en)
Inventor
Michael Mager
Markus Mechtel
Harald Kraus
Nusret Yuva
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Deutschland AG
Original Assignee
Bayer AG
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 Bayer AG filed Critical Bayer AG
Publication of EP1363979A1 publication Critical patent/EP1363979A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • 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
    • 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
    • C09D183/14—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
    • Y10T428/2995—Silane, siloxane or silicone coating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31652—Of asbestos
    • Y10T428/31663—As siloxane, silicone or silane

Definitions

  • the present invention relates to a method for producing sol-gel condensates using aqueous silica sols, and to their use for coating inorganic or organic substrates.
  • Sol-gel condensates which are based on, for example, can be obtained by co-condensation of SiO 2 nanoparticles with alkyltrialkoxysilanes, such as, for example, methyltrimethoxysilane
  • Plastic surfaces can be cured to inorganic coatings with high scratch resistance.
  • These sol-gel condensates are prepared by reacting methyltrimethoxysilane with an aqueous dispersion of SiO nanoparticles (aqueous silica sol) in the presence of organic solvents, such as e.g. in US-A 4,476,281.
  • organic solvents such as e.g. in US-A 4,476,281.
  • organic solvents is necessary because the hydrophobic alkyl radical means that neither the alkyltrialkoxysilanes used nor their hydrolysis and condensation products are completely miscible with water.
  • the organic residues can be chemically linked to the inorganic network by using polyfunctional organosilanes.
  • Polyfunctional organosilanes as described for example in EP-A 0 947 520, are linear, branched or cyclic monomeric organosilanes which have at least two silicon atoms with hydrolyzable and / or condensation-crosslinking groups, the silicon atoms each having at least one carbon atom via a linking Unit are connected.
  • polyfunctional organosilanes in which the linking unit is a cyclic siloxane, for example cyclo- ⁇ OSi [(CH 2 ) 2 Si (OH) (CH 3 ) 2 ] ⁇ are the starting materials material for the production of sol-gel condensates of particular interest, since for example sol-gel coatings with a scratch resistance similar to that of glass can be produced (see EP-A 0 947 520). These scratch-resistant coatings are of particular interest in the production of automotive coatings. In addition, such sol-gel coatings are notable for their pronounced hydrophobicity, which enables them to be used to produce, for example, anti-graffiti or fouling-release coatings (for example EP-A 96 72 53).
  • the polyfunctional organosilane is usually not reacted alone, but in combination with metal alkoxides and / or nanoparticles.
  • the hydrophobicity and the hardness of the resulting coating can be adjusted as required by a suitable choice of the proportions. So far, it has been a major disadvantage that the reaction of the polyfunctional organosilanes with SiO 2 nanoparticles in the presence of metal alkoxides was only possible by using solvent-containing SiO 2 nanoparticle dispersions, so-called organosols (eg EP-A 0 947 520) ).
  • organosilanes are completely immiscible with water and therefore also incompatible with aqueous dispersions of SiO 2 nanoparticles (aqueous silica sols).
  • aqueous silica sols aqueous dispersions of SiO 2 nanoparticles
  • the preparation of organosols is much more complicated than the corresponding aqueous silica sols, which are available on the market as commercial products (eg Levasil® ®, Bayer AG, Leverkusen).
  • the object of the present invention was therefore to provide a process which enables aqueous silica sols to be incorporated into sol-gel condensates based on polyfunctional organosilanes.
  • Organosilanes are miscible.
  • the present invention therefore relates to a method for producing sol-gel condensates, characterized in that
  • Silanol groups can condense either with themselves or with alkoxysilyl groups still present with the elimination of water or alcohol with the formation of Si-O-Si bonds.
  • the SiO 2 nanoparticles contained in the silica sol have a reactive surface, which is also available for reaction with the silicon alkoxides or their hydrolysis products.
  • Suitable polyfunctional organosilanes for the process according to the invention are linear, branched or cyclic monomeric organosilanes which have at least two silicon atoms with hydrolyzable and / or condensation-crosslinking agents Have groups, whereby the silicon atoms are each connected via at least one carbon atom via a linking structural unit.
  • Preferred polyfunctional organosilanes have the general formula (I)
  • ⁇ R2 z , ⁇ R> 3 J and R 4 are independently a CrCs alkyl radical or phenyl radical, where R and R can also be H, a, b independently of one another 0, 1 or 2 and c, d or e, f independently from each other are greater than or equal to 1, and
  • X is the bridging unit, a linear, branched or cyclic siloxane, carbosilane or carbosiloxane.
  • R 5 , R 6 and R 7 are independently of one another C 1 -C 4 -alkyl radicals, where R 5 is also the same
  • Can be H, h is 0.1 or 2, and g is an integer from 1 to 4, and i is an integer from 3 to 10.
  • cyclic carbosiloxanes are compounds of the formulas (Ula) to (Ille) in which R 8 is methyl or ethyl:
  • oligomers of the cyclic carbosiloxanes mentioned in WO 98/52992 can of course also be used as polyfunctional organosilanes in the process according to the invention. It is also possible to use mixtures of different cyclic monomeric or oligomeric carbosiloxanes.
  • Aqueous silica sols which are suitable for the process according to the invention essentially consist of a dispersion of amorphous, predominantly SiO 2 -containing nanoparticles with an average primary particle size of preferably 5 to 500 nm, which moreover are largely present as individual particles. Average primary particle sizes of 5 to 100 nm are particularly preferred for the production of transparent coatings.
  • the aqueous silica sols can be stabilized acidic or basic. The pH of the silica sol can be adjusted if necessary by adding acids or bases.
  • the concentration of the aqueous used can be any concentration of the aqueous used.
  • Silica sols can be increased by distilling off at normal pressure and elevated temperature or at reduced pressure and optionally elevated temperature. Before- therefore, the content of SiO 2 nanoparticles in the aqueous silica sols is 20 to 80% by weight, particularly preferably 30 to 60% by weight.
  • Suitable silicon alkoxides which can be reacted with the aqueous silica sol by the process according to the invention are preferably those of the general formula (IV),
  • a 0, 1, 2 or 3
  • R 9 represents an optionally substituted alkyl or aryl radical
  • R 10 is a to C 3 alkyl group.
  • a is 0 or 1
  • R 9 represents a methyl radical
  • R 10 is a methyl or ethyl radical.
  • the silicon alkoxide is firstly dissolved in a suitable medium dissolved, for example, alcohol, then the aqueous silica sol is added with stirring. After the addition has ended, the reaction mixture is stirred until it is homogeneous, ie there is no longer any emulsion or precipitation is visible. Finally, in the second step, the polyfunctional organosilane is added, which can optionally be previously dissolved in a suitable solvent.
  • sol-gel condensates composed of polyfunctional organosilanes, metal alkoxides and SiO 2 nanoparticles can be varied over a wide range.
  • the sol-gel condensates produced according to the invention preferably have the following theoretical composition, the calculation being based on complete hydrolysis and condensation:
  • Metal alkoxide (s) and SiO 2 nanoparticles are used in a weight ratio of 10: 1 to 1:10.
  • sol-gel condensates produced according to the invention particularly preferably have the following composition:
  • the solids content is adjusted to 10 to 50% by weight, preferably to 15 to 45% by weight, by adding an organic solvent.
  • the solvent which should be at least partially miscible with water, is preferably added before or during the preparation of the sol-gel condensate according to the invention.
  • the resulting solids content of the sol-gel condensate can be calculated beforehand from the proportions by weight of the individual components, taking into account the weight loss of the polyfunctional organosilane and the metal alkoxide through hydrolysis and condensation (the theoretical weight loss of Si (OC 2 H 5 ) 4 is, for example, 72% by weight).
  • the addition of organic solvents is also advantageous for the production of homogeneous coatings from the sol-gel condensates produced according to the invention.
  • the addition of organic solvents prevents segregation from occurring in the (inorganic) coating which forms.
  • the addition of organic solvents which are at least partially miscible with water and have a boiling point of at least 80 ° C. is particularly advantageous.
  • These solvents particularly preferably form azeotropic mixtures with water, as a result of which the sol-gel condensates can be freed of excess water by distillation at atmospheric pressure and elevated temperature or in vacuo at an optionally elevated temperature by azeotropic distillation.
  • the sol-gel condensate can be redissolved by removing volatile solvents.
  • sol-gel condensates produced from one or more polyfunctional organosilanes by the process according to the invention are particularly suitable for coating inorganic or organic substrates. After application, which can be done using all common techniques (e.g. painting, spraying, rolling,
  • the volatile components are evaporated at -10 ° C to 200 ° C and the sol-gel condensate is hardened on the surface.
  • inorganic coatings of high weather resistance, scratch resistance and chemical resistance can be obtained on metals, ceramics, glass, wood and plastics.
  • substrates that already have an organic coating, such as a polyurethane layer can be made with the ones produced according to the invention Sol-gel condensates are coated. Because of the nanoparticles contained in the sol-gel condensates, the coatings produced with the sol-gel condensates obtained according to the invention are very resistant to cracking due to moisture and / or temperature fluctuations.
  • sol-gel condensates produced according to the invention can be used, for example, for coating vehicles, which are then significantly less sensitive to scratches (for example by cleaning in a car wash).
  • sol-gel condensates produced according to the invention can also be used for the inorganic modification of organic polymers, which are then used, for example, as moldings or coatings.
  • the sol-gel condensate according to the invention can, for example, either be mixed directly with the organic polymers or else the condensate (Al or B1) obtained from the reaction of an aqueous silica sol with a silicon alkoxide is first mixed with the organic polymers and only then according to the invention with a implemented polyfunctional organosilane.
  • the condensate Al or B1 is preferably mixed with the organic polymers and only then reacted with a polyfunctional organosilane.
  • the proportion of organic polymers in the cured coating or in the molded parts is preferably between 10 and 90%, particularly preferably between 30 and 70%. embodiments
  • the D4-diethoxide oligomer used a condensation product of monomeric cyclo- ⁇ OSi [(CH 2 ) 2 Si (OEt) 2 (CH 3 )] ⁇ 4 , was prepared as described in WO 98/52992, cyclo- ⁇ OSi [(CH 2 ) Si (OH) (CH 3 ) 2 ] ⁇ 4 was prepared in accordance with the teaching of US Pat. No. 5,880,305.
  • the aqueous silica sols used were Levasil ® 200/30 and 200S / 30 from Bayer AG, Leverkusen, Germany.
  • Levasil ® 200/30 is an anionically stabilized dispersion of amorphous
  • SiO 2 nanoparticles (30% by weight SiO 2 in the delivery form), the mean particle size being 15 nm and the BET surface area being 200 m 2 / g.
  • the pH of Levasil ® 200/30 was adjusted from 9 to 2 by adding concentrated hydrochloric acid.
  • Levasil ® 200S / 30 is a corresponding dispersion, cationically stabilized with aluminum salts.
  • the pH of Levasil ® 200S / 30 was adjusted from 3.8 to 2 by adding concentrated hydrochloric acid.
  • the aqueous silica sols with a higher solids content were prepared by condensing water in vacuo (rotary evaporator).
  • Desmophen A665 BA / X is a polyol based on polyacrylate used for polyurethane coatings from Bayer AG, Leverkusen, Germany.
  • the moisture resistance of the inorganic lacquers produced from the sol-gel condensates was tested by application to a test plate which contained one in the
  • Example 3 The sol-gel condensate obtained according to Example 1 was applied by spraying to an automobile sheet and, after being left at room temperature for 10 minutes, was finally cured for 10 minutes at 80 ° C. and 30 minutes at 130 ° C. (dry layer thickness approx. 3 ⁇ m). After cooling, the test plate was distilled at 50 ° C for 7 days. Water stored. There were no cracks in the transparent, inorganic top layer.
  • Example 3
  • sol-gel condensate from example b) was applied to a glass plate using doctor blades (gap width 120 ⁇ m) and then cured for 10 min at room temperature and 1 h at 130 ° C.
  • a homogeneous, highly transparent inorganic lacquer was obtained which had a pencil hardness of 5H.
  • Example 3 As described in Example 3, a sol-gel condensate was produced, but using 1-pentanol as the solvent instead of 1-butanol. After application and curing as described in Example 4, a homogeneous, highly transparent inorganic lacquer was obtained which had a pencil hardness of 4H.
  • aqueous p-toluenesulfonic acid solution 0.3 g were added with stirring. After stirring the reaction mixture at room temperature for 1 h, a polycarbonate plate and a glass plate were then coated by means of doctor blades (120 ⁇ m gap width). After curing (10 min at room temperature, 60 min at 130 ° C in a forced air oven), a homogeneous film of excellent transparency and high hardness was obtained (pencil hardness 4 H, on glass). The coating on the polycarbonate plate was examined by TEM, and an excellent distribution of the SiO 2 nanoparticles in the inorganic matrix (from TEOS and D4-diethoxide oligomer) was found. The TEM images are documented in the appendix for clarification.
  • Condensate modified polymer The inorganically modified polymer prepared according to c) was applied by spraying to an automobile sheet instead of the conventional topcoat (clearcoat) and then cured for 5 min at room temperature and 30 min at 140 ° C. After cooling, the test plate was distilled at 50 ° C for 7 days. Water stored. There were no cracks in the transparent coating.

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

Abstract

La présente invention concerne un procédé permettant la préparation de condensats sol-gel par utilisation de sols de silice aqueux, ainsi que leur utilisation pour le revêtement de substrats minéraux ou organiques.
EP02702272A 2001-01-23 2002-01-16 Procede de preparation de condensats sol-gel a base d'organosilanes a fonctions multiples, et leur utilisation Withdrawn EP1363979A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10102739 2001-01-23
DE2001102739 DE10102739A1 (de) 2001-01-23 2001-01-23 Verfahren zur Herstellung von Sol-Gel-Kondensaten auf Basis polyfunktioneller Organosilane sowie deren Verwendung
PCT/EP2002/000362 WO2002059225A1 (fr) 2001-01-23 2002-01-16 Procede de preparation de condensats sol-gel a base d'organosilanes a fonctions multiples, et leur utilisation

Publications (1)

Publication Number Publication Date
EP1363979A1 true EP1363979A1 (fr) 2003-11-26

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EP02702272A Withdrawn EP1363979A1 (fr) 2001-01-23 2002-01-16 Procede de preparation de condensats sol-gel a base d'organosilanes a fonctions multiples, et leur utilisation

Country Status (7)

Country Link
US (1) US6673458B2 (fr)
EP (1) EP1363979A1 (fr)
JP (1) JP2004528402A (fr)
CA (1) CA2435201A1 (fr)
DE (1) DE10102739A1 (fr)
MX (1) MXPA03006482A (fr)
WO (1) WO2002059225A1 (fr)

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CA2435201A1 (fr) 2002-08-01
MXPA03006482A (es) 2004-05-24
DE10102739A1 (de) 2002-07-25
JP2004528402A (ja) 2004-09-16
US20020099161A1 (en) 2002-07-25
WO2002059225A1 (fr) 2002-08-01
US6673458B2 (en) 2004-01-06

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