Classifications

• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
  • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
  • C03C25/10—Coating
  • C03C25/104—Coating to obtain optical fibres
  • C03C25/106—Single coatings
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
  • C03C25/10—Coating
  • C03C25/24—Coatings containing organic materials
  • C03C25/40—Organo-silicon compounds

Definitions

• the present invention relates to a treatment composition for a glass, in particular a flat glass or a hollow glass (bottles, flasks, etc.), or a glass in the form of fibers, for improving the mechanical strength of said glass by healing surface defects thereof. It also relates to the corresponding treatment processes, as well as to the glasses thus treated.
• a water-based treating agent comprising: (I) an aqueous-based composition containing organopolysiloxanes, prepared from an alkoxysilane having a functional group such as amino, alkylamino, dialkylamino, epoxy, etc., and alkoxysilanes selected from trialkoxysilanes, dialkoxysilanes and tetraalkoxysilanes; and
• a silicon-free component selected from waxes, partial esters of fatty acids and / or fatty acids, and which may contain a surfactant.
• the temperature of the glass surface during the application of the treatment agent amounts to at least 30 ° C., in particular being from 30 ° to 150 ° C.
• this coating agent as a second layer is described, the first layer being obtained from a treatment agent containing a trialkoxysilane and / or a dialkoxysilane and / or a tetraalkoxysilane or their hydrolysis and / or condensation products.
• US Pat. No. 6,403,175 B1 discloses a cold treatment agent for hollow glass containers to reinforce them on the surface.
• This water-based agent contains at least the following components: a trialkoxysilane, a dialkoxysilane and / or a tetraalkoxysilane, their hydrolysis products and / or their condensation products; a water-soluble mixture of a polyol and a crosslinking agent of the polyol, the layer of cold treatment agent thus applied being then subjected to crosslinking over a temperature range between 100 and 35O 0 C.
• the present invention therefore firstly relates to a composition for treating the surface of a glass, in particular a flat glass or a hollow glass, or a glass in the form of fibers, said composition being capable of being applied in a thin layer to said glass, characterized in that it comprises, in an aqueous medium, the following constituents (A) and (B):
• At least a part of the compounds comprising at least one RO- function attached to a silicon atom that may be in a hydrolysed form resulting from a spontaneous prehydrolysis or hydrolysis occurring during the contact of the compound (s) with the aqueous medium .
• the alkyl radical for R is in particular a linear or branched C 1 -C 6 alkyl radical.
• the functions f (A) and f (B ) can in particular be chosen from the functions -NH 2 , -NH-, epoxy, vinyl, (meth) acrylate, isocyanate, alcohol.
• thermal pathway includes the polymerization at room temperature which may be possible in some cases.
• Bisphenol derivatives (A) (compounds having no SiOR or SiOH function);
• A is a hydrocarbon radical which has at least one group selected from amino, alkylamino, dialkylamino, epoxy, acryloxy, methacryloxy, vinyl, aryl, cyano, isocyanato, ureido, thiocyanato, mercapto, sulfane or halogen groups; bonded to silicon directly or via an aliphatic or aromatic hydrocarbon radical; R 1 represents an alkyl group, in particular
• Ci-C 3 or A as defined above;
• R 2 represents a C 1 -C 8 alkyl group which may be substituted by an alkyl [polyethylene glycol] residue;
• x 0 or 1 or 2.
• the functions f (A) of the constituent (A) are -NH 2 and / or -NH- functions
• the functions f (B ) of the constituent (B) are epoxy functions
• the ratio of the number of functions -NH of the component (A) to the number of epoxy functions is between 0.3: 1 and 3: 1, inclusive, in particular between 0.5: 1 and 1.5: 1 inclusive.
• composition according to the invention which comprises 3-aminopropyltriethoxysilane as component (A) and glycidoxypropylmethyl-diethoxysilane as component (B), the latter being advantageously introduced in the prehydrolysed state.
• component (A) and (B) Once introduced into the aqueous medium, the constituents (A) and (B), at least one of which has at least one -SiOR function, undergo a hydrolysis of the function or functions -SiOR in -SiOH, in a period of longer or shorter after contact with water.
• an acid such as acid hydrochloric acid or acetic acid to catalyze
• the composition is intended to be applied to the glass to be treated, and forming a thin film by polymerization or polycondensation reaction of the functions f ⁇ A> of component (A) on the functions f ⁇ B) of component (B).
• the polycondensation product reacts with the glass via the SiOH and SiOR radicals, thus making it possible to cure the surface defects of the latter: glazes, cracks, shocks, etc.
• the film thus formed is intended to improve the mechanical strength of the glass.
• composition according to the invention may furthermore comprise: (Cl) at least one polymerization or polycondensation catalyst of the constituents (A) and (B); and or
• the constituent (Cl) is or comprises a tertiary amine, such as triethanolamine and diethanolamine propanediol.
• tertiary amines those of formula (III):
• R 7 wherein R 5 to R 7 each independently represent an alkyl or hydroxyalkyl group.
• the presence of at least one catalyst makes it possible to reduce the duration and temperature of polymerization, avoiding, in the case of coating vials or the like, the use of an additional polymerization arch and making it possible to work at the temperature of the bottles. leaving the annealing arch (at 15O 0 C for example), as will be described below.
• Radical polymerization initiators are for example mixtures comprising benzophenone, as Irgacure ® 500 marketed by the company "CIBA SPECIALTY CHEMICALS.”
• composition of the invention may furthermore comprise:
• waxes mention may be made of polyethylene waxes, whether or not they are oxidized.
• the waxes, partial esters of fatty acids and fatty acids may be introduced into the composition in the state associated with a surfactant.
• the protective agents (D) are thermoplastic and have elastic slip properties. Their inclusion in the formed thin film contributes to the protection against scratches and wear and handling frictions.
• the emulsion polymers (E) are in particular chosen from emulsion acrylic copolymers, such as those of the “Hycar ® " series sold by the company "NOVEON”.
• surfactant (F) there may be mentioned polyoxyethylene fatty ethers, such as C IS H 35 (OCH 2 CH 2) IO OH, known under the name of "Brij ® 97” and that triblock copolymers poly (ethylene oxide) - poly (propylene oxide) -poly (ethylene oxide).
• the surfactants used in the examples below are also mentioned.
• the composition according to the invention can thus comprise, in an aqueous medium, for a total of 100 parts by weight: up to 25 parts by weight of component (A); up to 25 parts by weight of component (B); 0 to 25 parts by weight of component (Cl) as defined above;
• component (D) 0 to 25 parts by weight of component (D) as defined above;
• component (E) 0 to 25 parts by weight of component (E) as defined above;
• component (F) 0 to 25 parts by weight of component (F) as defined above, the aforementioned amounts being indicated as solids, and when an agent is introduced in the form of a solution or aqueous emulsion, the amount of water of this solution or emulsion then forming part of the aqueous medium of the composition.
• the subject of the present invention is also a process for treating the glass surface to improve its mechanical strength by healing surface defects, characterized in that a thin film of the composition such as as defined in one of claims 1 to 15 in a thickness of up to 3 microns, and that a polymerization or polycondensation of said composition is conducted.
• composition according to the invention may be prepared for its application by mixing its constituents, generally at the time of use, in various ways:
• composition according to the invention contains the constituents (A) + (B) + water
• it can be prepared by first mixing (A) + (B), then combining this mixture with the water at the time of mixing. 'employment.
• catalysts and / or additives are present, they can be mixed with water, before mixing with (A) + (B) at the time of use. It is also possible, in the case where one of the constituents (A) or (B) has been hydrolyzed, to incorporate the additives into the unhydrolyzed component.
• the application of the composition is advantageously carried out by spraying or dipping ("dip coating").
• a drying for example for a few seconds, then a passage under UV lamps, the UV treatment having a duration for example of a few seconds to 30 seconds.
• the thermal polymerization or polycondensation can be carried out at a temperature of, for example, 100 to 200 ° C. for 5 to 20 minutes.
• the temperature and the duration of the treatment depend on the system used.
• the glass to be coated is a hollow glass
• composition when the composition does not contain a catalyst, by passing the hollow glass in a polymerization arch at a temperature of 100 to 22O 0 C for a period of time of a few seconds to 10 minutes;
• the present invention also relates to a flat glass or hollow glass treated with a composition as defined above, according to the process as defined above, as well as on glass fibers, in particular optical fibers (for example useful for dental lamps) treated with a composition as defined above, according to the process as defined above.
• the present invention also relates to the use of a composition as defined above, for improving the mechanical strength of hollow glass by healing glass surface defects.
• the following examples illustrate the present invention without, however, limiting its scope. In these examples, parts and percentages are by weight unless otherwise indicated.
• the "SR610” is a polyethylene glycol 600 diacrylate sold by the company "CRAY VALLEY”
• the mixture “CRAY VALLEY” is a mixture constituted by 67% of "SR610” as defined above and 33% of an aliphatic oligomer diacrylate marketed under the name "CN132" by the company CRAY VALLEY.
• Irgacure ® 500 is the trade name of a radical polymerization initiator marketed by "CIBA", constituted by
• EXAMPLE 1a Flat glasses with a coating layer formed by drying and UV curing.
• a glass coating composition was prepared by hydrolyzing the silane of the formulation in water for 24 hours and then adding the other components of the formulation.
• the composition thus obtained was deposited on a batch of flat glasses (70 ⁇ 70 ⁇ 3.8 mm) on which defects had been created by Vickers indentation with a diamond pyramidal tip and an applied force of 50N.
• the deposit was made by immersion ("dip-coating") at a controlled speed of 500 mm / min to ensure a uniform thickness. This deposit was made 24 hours after indentation so that the crack propagation was stabilized and the constraints around the defect created were relaxed.
• the glasses were then dried for 10 minutes at 100 ° C., and then the coated layer was subjected to UV polymerization for 25 seconds, the characteristics of the UV emitter being as follows: distance from the surface of the substrate by compared to the lamp: 5 cm; iron-doped mercury lamp (UVH Strahler type lamp
• Tripod bending was broken into glasses thus coated, extending the created defect. This test was carried out without UV aging and climatic formed coatings
• a batch of 10 flat glasses was not coated and served as a control.
• the tripod breaking results express the modulus of rupture (MOR) (MPa) and serve as an assessment of the performance of the composition reinforcement.
• the reinforcement results for the coating represent the difference of the modulus of rupture in the bending test between the flat control glasses and the treated flat glasses.
• the formulation of this example shows a very strong reinforcing effect of weakened glasses, this reinforcement being in fact 107.8% compared to uncoated indented flat glasses.
• the graph in Figure 1 expresses the percentage of cumulative failure as a function of the modulus of rupture in MPa.
• the curve representing the 10 coated flat glass samples is shifted towards the highest rupture moduli with respect to the curve of the ten uncoated flat glass samples.
• the coating formed from the composition of this example therefore gives greater mechanical strength to the glass.
• Copolymer surfactant marketed under 0.2 the name “Gantrez”
• a glass coating composition was prepared by the following procedure: The two silanes were premixed for 5 minutes, then the water was added and the silanes were hydrolyzed with vigorous stirring for 30 minutes. Then we added the wax.
• Example 1 (c) The same test as in Example 1 (c) was carried out on the glasses thus coated. The results obtained are presented in the
• a first can containing aminopropyltriethoxysilane and glycidoxypropylmethyldiethoxysilane were prepared and mixed for 5 to 7 minutes (Example 3a) or 10 minutes (Examples 3b, 3c: 3d) and, on the other hand, on the other hand, a second can containing the polyethylene wax, the polyurethane and the water, and then the contents of the two cans were mixed 30 minutes before application.
• Example 2 (b) The procedure was then as in Example 2 (b), except that the heat treatment (polymerization) was carried out at 200 ° C. for 20 minutes.
• Example 1 (c) The same test as in Example 1 (c) was carried out on the glasses thus coated from the composition of Example 3b.
• the curve representing the ten coated flat glass samples is shifted to the highest failure modules by compared to the curve of the ten uncoated flat glass samples.
• the coating formed from the composition of Example 3b therefore gives greater mechanical strength to the glass.
• the reinforcement provided by the coating based on the composition of Example 3b is not modified after the aging tests WOM and CV.
• a composition is prepared as in Example 3a, except that pre-hydrolysis of the two silanes (Example 4a) or glycidoxypropylmethyldiethoxysilane (Example 4b) is carried out with all the water for 15 minutes.
• a composition was prepared as in Example 3a, except that 0.15 parts of triethanolamine (Example 5a) was added to the second can.
• Example 3c A composition as in Example 3c was also prepared except that 0.075 part of triethanolamine and 0.075 part of diethanolamine propanediol (Example 5b) were added to the second can.
• 3-aminopropyltriethoxysilane and glycidoxypropylmethyl- diethoxysilane is complete.
• the prehydrolysis of glycidoxypropylmethyldiethoxysilane does not affect the hydrolysis reaction kinetics of the two silanes.
• pre-hydrolysis of glycidoxypropylmethyldiethoxysilane influences reinforcement over time.
• the flat glass reinforcement results as a function of the maturation time (Ih, 3h and 6h or 8h) for the formulation of Examples 3a and 4b are illustrated in Figures 6 and 7, respectively.
• Table 5 Summary table of the reinforcements with the formulation of Examples 3a and 4b to the tripod test on flat glasses indented with 5ON
• the reinforcement on samples of flat glasses indented at 50 N degrades over time. From 3 hours of life of the mixture, the reinforcement without pre-hydrolysis of glycidoxypropylmethyl-diethoxysilane ( simultaneous hydrolysis) and with pre ⁇ hydrolysis of glycidoxypropylmethyldiethoxysilane falls.
• the viscosity of the formulation of Examples 3 and 4 with or without pre-hydrolysis of glycidoxypropylmethyl-diethoxysilane is dependent on the temperature at which the mixture is subjected (20 ° C. or 40 ° C.). It changes all the faster as the temperature is high.
• the viscosity of the formulation is also dependent on the nature of the polyethylene wax used (OG25 or GK6006). In the presence of GK6006 (Example 3d), the mixture appears stable over time while an increase in viscosity is observed when the formulation contains 1OG25.
• a tertiary amine triethylamine makes it possible to shorten the polymerization time in half (10 minutes against 20 minutes) and to reduce the polymerization temperature by 50 ° C. (150 ° C. against 200 ° C.) while preserving a level of about 90% reinforcement.
• the defects on the edges are less severe than the defects created with an indentation of 50 N.
• the cutting and the shaping of the glass create smaller defects on the edges.
• a force of 5 N is applied during indentation.
• the size (indentation at 50 N or 5 N) and the nature of the defect (indentation or shaping) lead to different reinforcement values for the coating of Example 3a.
• the glass coating compositions were prepared by the following procedure.
• Epoxysilane was hydrolyzed for 10 minutes in water, then aminosilane was added and hydrolyzed for 20 minutes before adding GK 6006 wax.
• the test was conducted on a bottle production line using a 16 section IS machine, 32 molds, 300 Burgundy and 410 g.
• the bottles are taken out of the arch before the cold treatment, then treated by cold spraying under the following conditions: bottles upside down on spinners, two nozzles for treating respectively the bottom and the barrel of the bottles: the spray nozzle specific for the barrel was 16 cm from the bottle; its spray axis was 11 cm from the bottom of the same bottle.
• the nozzle for the bottom was located 16 cm from the bottle; it sprayed the bole up to 3 cm from the bottom.
• the rotational speed of the spinner was 120 rpm. ; the spraying times were chosen to make complete turns.
• the atomizing air pressure was 5.5 bar.
• Example 11a The parameters were set to obtain a slip angle of about 8 ° with the formulation of Example 11a: - Nozzle drum: 4 liters / h;
• bottles taken are treated by spraying (cold bottles), dried for 15 minutes, then subjected to a study heat treatment of 20 minutes at 200 ° C.
• the other bottles serve as a control.
• Each series consists of 320 bottles (10 bottles per mold). The entire surface of the bottles is treated, as well as the bottom. The thickness of the coating is 150 to 300 nm.
• Bottles treated with the formulation of Example 10a have a sliding angle of 8 °; those treated with the formulation of Example 10b have a sliding angle of 20 °. the the
• the resistance of the bottles is evaluated by the internal pressure test (AGR device).
• the break histograms are shown in Figures 8 and 9 and the average breaking pressures in Table 8 below.
• epoxysilane is solubilized for 5 minutes in water. Then the amino silane is added and mixed for 15 minutes. Finally, copolymer emulsion is added and mixed for 3 minutes.
• the coating compositions thus prepared were deposited on ION-indented glass samples by soaking these glasses in said compositions at 50 cm -1min -1 , followed by air drying of the samples for 10 minutes. then by heat treatment at 200 ° C. for 20 minutes.
• Example (c) was used as in the Example, the results obtained being presented in Table 9 below as well as in FIG. 10.

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Materials Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Geochemistry & Mineralogy (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• General Life Sciences & Earth Sciences (AREA)
• Paints Or Removers (AREA)
• Surface Treatment Of Glass Fibres Or Filaments (AREA)
• Surface Treatment Of Glass (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

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• 2004
  • 2004-07-02 FR FR0451430A patent/FR2872508B1/fr not_active Expired - Fee Related
• 2005
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  • 2005-07-01 BR BRPI0512877-3A patent/BRPI0512877A/pt not_active Application Discontinuation
  • 2005-07-01 JP JP2007518670A patent/JP2008504210A/ja active Pending
  • 2005-07-01 US US11/631,326 patent/US20080050529A1/en not_active Abandoned
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  • 2005-07-01 MX MX2007000010A patent/MX2007000010A/es active IP Right Grant
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