Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/12—Organo silicon halides
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
  • C07F7/1804—Compounds having Si-O-C linkages

Definitions

• the present invention relates to the field of surface treatments. It relates to a composition and a method for treating the surface of substrates using this composition.
• the subject of the invention is also a compound and its preparation process.
• the subject of the invention is substrates capable of being obtained by said surface treatment process.
• soiling can also present a non-negligible risk, for example due to poor vision due to a reduction in transparency. Efforts are then necessary to maintain or restore a minimum degree of cleanliness, which generates a certain cost.
• the degree of soil retention is generally attributed to the wettability of the substrates by polar and non-polar liquids.
• the wettability of a substrate by a liquid is characterized by the contact angle formed by a drop of this liquid on the substrate.
• a high angle and in particular greater than 90 ° testifies to the non-wettability of the substrate by the liquid.
• US Pat. No. 5,523,161 teaches a poorly wettable glass substrate obtained by treatment with a perfiuoroalkylalkylsilane.
• the treatment is made more durable by mixing the perfiuoroalkylalkylsilane with silanes capable of hydrolysis.
• Such perfluoroalkylalkylsilane films are also described in document EP 692,463.
• the abrasion resistance is improved by depositing these films over an inorganic undercoat.
• EP 491 251 and EP 492 545 disclose monomolecular films of perfluoroalkylalkylsilanes which can have an ether, ester or carbonyl function between the perfluoroalkyl group and the alkyl group.
• These proposed anti-fouling treatments give the substrates thus coated a character which is poorly wettable by polar and non-polar liquids, therefore both hydrophobic and oleophobic. Such liquids then form drops having a large contact angle. It is generally accepted that when such substrates are mounted vertically or exposed to rain and wind, for example to form the facade of a building or a car windshield, gravity and / or aerodynamic forces are sufficient on their own to remove water drops.
• a surface treatment which overcomes the difficulties described above and which is also preferably rapid, easy to implement, inexpensive and not very toxic.
• the problem is solved by a surface treatment giving a substrate an improved resistance to dirt and grease and oil.
• a substrate thus treated has a self-cleaning character.
• Self-cleaning character is understood to mean easy removal of soiling, by simple trickling of water for example, without mechanical assistance.
• a first subject of the invention is then a composition comprising a compound of formula (I):
• R f represents a linear or branched chain perfluorinated alkyl radical containing 1 to 20 carbon atoms, preferably 6 to 16 carbon atoms;
• B represents a bivalent group which may contain 1 to 3 atoms of oxygen, sulfur and / or nitrogen;
• Ro represents 1 to 100, preferably 5 to 20 oxyalkylene groups, preferably oxyethylenic or oxypropylene groups linked to group B by a carbon atom;
• Z is a hydrogen atom or, when B carries a hydroxyl group, a straight or branched chain alkyl group having 1 to 6 carbon atoms; and a compound of formula (II):
• R which: m is an integer from 0 to 10, preferably 0 to 3; R each independently of one another represents a linear or branched alkyl group having 1 to 6 carbon atoms; p is an integer from 0 to 2, preferably 0;
• a each independently of one another represents a halogen, preferably chlorine, or an alkoxy group containing 1 to 6 carbon atoms, preferably methoxy, ethoxy, propyloxy and / or isopropyloxy; and
• Y represents a group comprising an isocyanate, epoxide, carboxylic acid or alcohol function
• Y can also represent Si (R p ) (A) 3 .
• p when m is different from zero, and a group A when m is equal to zero; and / or their reaction product.
• the compound of formula (I) will be chosen from the well-known nonionic fluorinated surfactants, for example FORAFAC® 1110D from ATOFINA or else ZONYL® FSN or FSO from Du Pont or even UNIDYNE DS 401 from DAIKIN.
• the compound of formula (I) can be a primary alcohol or a secondary alcohol.
• the secondary alcohol can be obtained for example by reaction of a fluorinated epoxide on a polyglycol ether such as CH 3 O (C 2 H 4 O) n -C 2 H 4 OH.
• derivatives having an isocyanate or epoxide function are for example ⁇ -isocyanatopropyltriethoxysilane (SILQUEST A1310 silane from Witco), COATOSIL 1770 from Witco or also glycidyl-3-oxypropyl-triethoxysilane (GLYEO from H ⁇ ls / Sivento).
• SILQUEST A1310 silane from Witco
• COATOSIL 1770 from Witco
• GLYEO glycidyl-3-oxypropyl-triethoxysilane
• Such a composition is particularly useful for the surface treatment of substrates.
• the composition contains in combination with an anhydrous solvent 1 to 50%, and in particular 10 to 40% by weight of compound of formula (I) and (II) and / or their reaction product.
• suitable anhydrous solvents are, for example, esters such as ethyl, butyl or isopropyl acetates, ketones such as acetone, methyl ethyl ketone or also methyl isobutyl ketone.
• the composition can comprise several compounds from each category.
• the composition can also be added with the various usual additives.
• this composition can be diluted by the introduction of another solvent chosen from water, alcohols and their mixtures.
• Such a composition can comprise 0.05 to 5% and in particular 0.1 to 2% by weight of the compounds mentioned.
• the composition is in the form of an aqueous emulsion.
• the invention also relates to a process for the preparation of such a composition. This process includes the step of:
• a hydrolysis agent such as water is added for the hydrolysis of the alkoxysilane or halogenosilane functions.
• the method then includes the additional step of:
• the method further comprises the following steps:
• step (c) emulsification of the solution obtained in step (b), where appropriate in the presence of a surfactant or of a water-soluble polymer; and eventually
• the compound according to formula (III) can be obtained in particular by reaction of the alcohol function of a compound of formula (I), and with the group Y of the compound of formula (II) in the presence, where appropriate, of a catalyst.
• the solution of the compound in the synthesis solvent constitutes a preferred embodiment of the invention.
• Such a composition is obtained directly after the synthesis of the compound and does not require any subsequent separation step.
• the compound of formula (III) can however also be isolated in the form of a powder, a paste or a liquid, by total elimination of the synthetic solvent and then incorporated into other solvents or compositions.
• the isolated compound will be introduced into a suitable anhydrous solvent such as for example a solvent chosen from esters such as ethyl, butyl or isopropyl acetates, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone.
• a suitable anhydrous solvent such as for example a solvent chosen from esters such as ethyl, butyl or isopropyl acetates, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone.
• a suitable anhydrous solvent such as for example a solvent chosen from esters such as ethyl, butyl or isopropyl acetates, ketones such as acetone, methyl ethy
• the compound of formula (lu) can also be synthesized in situ at the time of application of a composition according to the invention comprising its precursors.
• compositions according to the invention further comprising other solvents such as water and / or alcohols such as methanol, ethanol or isopropanol, preferably ethanol or isopropanol.
• other solvents such as water and / or alcohols such as methanol, ethanol or isopropanol, preferably ethanol or isopropanol.
• methanol, ethanol or isopropanol preferably ethanol or isopropanol.
• a mixture of water and alcohol is used.
• the added water firstly has the task of serving as a hydrolysis agent for the alkoxysilane or halogenosilane groups.
• Alcohols generally represent good solvents for the products contained in the composition. These compositions are also particularly advantageous in terms of environmental protection and safety of implementation.
• compositions can be obtained for example by diluting the composition comprising an anhydrous solvent in a hydro-alcoholic solution.
• the hydroalcoholic solution contains from 0 to 100%, preferably from 10 to 90% by weight of alcohol.
• the addition of an organic or inorganic acid chosen, for example from acetic acid or hydrochloric acid is advantageous in that it catalyzes the hydrolysis of the halosilane or alkoxysilane functions.
• the anhydrous solvent composition can also be diluted in water. In this case, it may be advantageous to work in the presence of one or more surfactants and / or one or more water-soluble polymers.
• the solution is strongly stirred, for example by means of a high pressure homogenizer, then distilled in order to remove all or part of the anhydrous solvent.
• a stable aqueous emulsion is thus obtained.
• the reactions which take place when the composition is applied to the surface of a substrate are not precisely known. It seems however that the alkoxysilane or halosilane groups present in the composition are hydrolyzed under the effect of the hydrolysis agent into Si-OH groups, which can react with each other but also with the reactive groups present on the surface of the substrate example Si-OH groups in glass.
• the last type of reaction is also designated as chemical adsorption of the layer deposited on the substrate.
• the silane groups can also react intermolecularly to form a three-dimensional network comprising Si-O-Si bonds, thus imparting great hardness to the layer thus deposited.
• Another object of the invention relates to a method for treating the surface of a substrate, comprising the step of:
• the substrates are preferably thoroughly cleaned before surface treatment. Such cleaning considerably improves the adhesion properties, for example by activating the hydroxyl functions on the surface of a glass substrate.
• a hydrolysis agent such as water, for example being in the form of an aqueous-alcoholic solution or an aqueous emulsion.
• a hydrolysis catalyst such as an organic or mineral acid can optionally be added.
• the composition applied can also be in the form of a solution in an anhydrous solvent.
• the humidity in the air acts as a hydrolysis agent.
• composition as described can be applied to the substrates by suitable and known techniques, such as for example spraying, brushing, coating, impregnation, immersion, at a concentration ranging from 0.05 to 5%, preferably from 0.1 to 2% of active material.
• the method further comprises a step of:
• step (ii) heat treatment of the substrate obtained after step (i) at a temperature between 50 and 200 ° C for a period between one second and 24 hours.
• the process is carried out using water as the hydrolysis agent.
• the heat treatment is shorter the higher its temperature. This heat treatment allows above all to evaporate the solvent. Thus, it will be recommended when the solvent has a high evaporation temperature.
• the hydrolysis agent is on the substrate to which the composition is applied.
• the subject of the invention is finally the substrate capable of being obtained by the method described above.
• Such substrates are generally mineral or organic substrates made of transparent material, on which the traces of dried drop residue are the most troublesome.
• These substrates may, prior to the surface treatment process according to the invention, have been the subject of another surface treatment, for example an anti-reflection treatment.
• the materials concerned are for example glass, polymethyl methacrylate and polycarbonate, but also all types of materials such as stone, brick, concrete, wood, tiles, leather or textiles.
• the substrates treated according to the process according to the invention have good resistance to oils and a self-cleaning character.
• EXAMPLE 1 20 parts of a 250 ml three-necked flask provided with a thermometric probe, of a refrigerant connected to the atmosphere by a CaCl 2 guard, 20 parts of FORAFAC 1110 oxyethylated fluorinated alcohol of structure C 6 F ⁇ 3 C are introduced. 2 H 4 O (CH 2 -CH 2 O) n H, with an average n of 11. This compound was synthesized by the action of ethylene oxide on alcohol C 6 F ⁇ 3 -C 2 H 4 OH with a BF 3 / ether catalysis. The dioxane produced by the reaction was removed with toluene which was then distilled.
• the oxyethylated alcohol is diluted with 42 g of anhydrous ethyl acetate, then the catalyst is added: 0.2 part of tin dibutyldilaurate. After inerting the reaction medium by sweeping with anhydrous nitrogen, the mixture is heated the solution at reflux at 77 ° C., then the stoichiometric amount is introduced relative to the OH group of 3- (triethoxy) silylpropylisocyanate of formula (CH 5 O) 3 Si (CH 2 ) 3 -
• the Si solution is obtained with 40% of active material of structure:
• This example describes the preparation of a composition for the in situ synthesis of the compound during application.
• 18 parts of FORAFAC 1110 fluorinated oxyethylated alcohol of structure: C 6 F ⁇ 3 C 2 H 4 O (CH 2 -CH 2 O) n H with an average n of 11 are introduced into a 125 ml bottle dissolved in 55 parts of ethyl acetate and 18 parts of tetraethoxysilane Si (OC 2 H 5 ) 4 from Aldrich are added. This gives the solution S 2 (40% dry extract) of a two-component mixture ready for use.
• This example describes the preparation of a composition for the in situ synthesis of the compound during application.
• 25 parts of FORAFAC 1110 fluorinated alcohol of FORAFAC 1110 structure C 6 F 13 C 2 H 4 O (CH 2 -CH 2 O) n H are introduced into a 125 ml flask with an average n of 11 which is dissolved.
• the solution S 3 (40% dry extract) is then obtained from a ready-to-use two-component mixture.
• This example describes the preparation of a mixture for the in situ synthesis of the compound during application.
• 25 parts of FORAFAC 1110 fluorinated oxyethylated alcohol with structure: C 6 F ⁇ 3 C 2 H 4 O (CH 2 -CH 2 O) n H with an average n of 11 are introduced into a 125 ml bottle.
• dissolved in 55 parts of ethyl acetate and 11.7 parts of HULS / SIVENTO GLYEO silane epoxy are added with structure:
• an oxyethylated surfactant 45 parts are introduced into a 100 ml three-necked flask provided with a temperature probe, a refrigerant and a dropping funnel.
• the Sc2 solution at 55% of active ingredient of structure is obtained: CH 3 (CH 2 ) ⁇ 7 - (OCH 2 CH 2 ), 0 O CONH (CH 2 ) 3 Si (OC 2 H 5 ) 3 .
• Oil resistance is characterized by the measurement of the contact angle of petrolatum, dodecane and tetradecane drops deposited on the treated substrate.
• a comparison measurement is carried out on an untreated glass substrate. The angle is measured using an ERMA Gl type goniometer.
• a drop of small volume ( ⁇ 1.5 ⁇ l) of oil is deposited on the treated substrate using a syringe controlled by a micrometric screw. The substrate is maintained in a horizontal position on a plate, the horizontality of which is controlled by a spirit level.
• the angle is measured at the two tangents at the contact points of the drop on the substrate. The average of these two angles over at least four drops is used.
• the self-cleaning character is determined using a variant of the so-called "spray test” described in standard AATCC 22-1989. It consists of pouring onto a treated substrate in accordance with the invention then soiled, fixed on a support inclined at 45 °, 50 ml of water from a funnel provided with a sprinkler in approximately 5 seconds and a height of approximately 20 cm.
• the substrates obtained by treatment with solutions according to the invention and the comparative examples are previously soiled by spraying vaseline oil colored red with organol type dye.
• the deposit made is of the order of 30 g / m 2 .
• the water is then passed in accordance with the test and the visual assessment of the result. We note in particular the persistence of stains of colored oils as well as the presence of residual drops of water. The results are shown in the following table.
• Comparative Example 1 is an alkoxysilane carrying a perfluorinated group and also carrying an ester and thioether group. It has a strongly oleophobic character as it emerges from the contact angles measured with respect to non-polar liquids. We therefore observe the appearance of small oil droplets when the substrate is soiled by the spraying of colored oil. However, this type of treatment does not allow the elimination of soiling by simple passage of water. Indeed, there remain small colored spots, which probably come from the drying of small water droplets containing impurities.
• Comparative Example 2 relates to a compound carrying hydrophilic groups, but not perfluorinated groups. It can be seen from the small contact angles measured that this compound is oleophilic. It is found that, in fact, the substrate is wetted by petroleum jelly without the formation of droplets. Furthermore, the substrate has a rather hydrophilic character. However, this character alone is not sufficient since we observe colored streaks after passing the water. Furthermore, the test on untreated glass demonstrates the unsatisfactory behavior of a substrate having an oleophilic and hydrophobic character.
• the substrates treated with the compositions according to the invention have very satisfactory results, namely the virtual absence of colored spots of petrolatum, and also small drops of water capable of subsequently reinforcing the effect. visual dirt on the substrate. It is assumed that this behavior is linked to the oleophobic and hydrophilic nature of these compositions.
• compositions according to the invention allow an effective anti-fouling treatment of substrates, consisting in removing dirt by simple passage of water.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Polyethers (AREA)
• Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)

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• 2001
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• 2002
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