FR2610917A1 - PROCESS AND COMPOSITIONS FOR TREATING GLASS SURFACES - Google Patents

Abstract

THE INVENTION CONCERNS THE TREATMENT OF GLASS SURFACES BY MEANS OF A PYROLYSABLE COMPOSITION TO DEPOSIT A COATING OF TIN OXIDE. THE PYROLYSABLE COMPOSITION CONTAINS A LIQUID COMPLEX OR A SOLUTION CONSISTING OF AN ORGANOCHLORINE STANNIC COMPOUND ASSOCIATED WITH AN ORGANIC MOLECULE SUCH AS AN ETHER OR A HETEROCYCLE. THIS COMPOSITION IS PARTICULARLY USEFUL FOR INDUSTRIALLY TREATING HOT GLASS CONTAINERS.

Description

PROCESS AND COMPOSITIONS FOR TREATMENT

OF GLASS SURFACES

  The present invention relates to a

  and the use thereof to improve the mechanical resistance of glass surfaces, in particular the external surfaces of hollow glass articles, such as bottles, flasks, jars and the like.

  It also relates to a method and

  for the treatment of flat glass.

  It is known in particular from the US-A-

  3,414,423 and US-A-3 420 693 for treating a glass surface with a titanium compound or a compound

  of pyrolyzable tin, that is to say, decomposable

  Titanium oxide or tin oxide on the glass surface, the temperature of which is higher than the pyrolytic temperature of the titanium or tin compound.

  It is also known from the patent BE-A-

  833,483 to treat the surface of glass objects with organotin halides of the formula: R Sn X3 (I) wherein R denotes a straight or branched chain alkyl radical containing up to 8 carbon atoms and X denotes a halogen. Among the compounds of

  (I), there may be mentioned methyl trihalides

  tin, ethyl-tin, propyl-tin, butyl-tin,

  of hexyltin, heptyltin and octyltin, in particular

  especially n-butyl tin trichloride.

  The above-mentioned tin compounds are most often applied to glass surfaces, in phase

steam or spray.

  The titanium compounds and tin compounds referred to in the aforementioned patents have various disadvantages when used for the treatment of glass surfaces at a temperature above their temperature.

pyrolysis.

  Thus, the halides of titanium and tin are unstable and hydrolyze easily in the presence of

  traces of moisture present in the ambient air, in

  very corrosive and toxic acids.

  Furthermore, organic titanium compounds, as well as organic tin compounds are often toxic, so their use is

  difficult, if not impossible, on an industrial scale.

  Finally, many organic compounds of

Titanium or tin are unstable.

  It has now been found that the abovementioned disadvantages can be overcome by using, for the treatment of glass surfaces, to improve their resistance to abrasion, especially their resistance.

  scratching, complexes containing tin

  with the formula Ru% R SnCly - Z (II) x y% Rm R where x is an integer 0 to 3, y is

  an integer equal to i to 4, provided that x + y -

  4, Z is oxygen, sulfur, phosphorus or nitrogen, R is a straight or branched chain alkyl radical which may contain 8 carbon atoms or a phenyl radical, R 'and R ", which may to be identical

  or different, denote an alkyl radical

  hydroxyl or phenyl or may form with Z a ring which may contain a heteroatom, and R '' 'which is only present in the complex when Z is phosphorus or nitrogen is an alkyl radical

  optionally hydroxylated or phenylated.

  The invention therefore relates to a process for treating

  glass surfaces with at least one complex of formula (II), as well as glass surface treatment compositions containing at least one

such complex.

  In a particular embodiment of the invention, a complex of formula (II) in which x 1, y-3, Z is oxygen, R is an n-butyl radical and R 'and Ru are alkyl radicals,

optionally hydroxylated.

  The complex of formula (II) is advantageously

  a complex in which x - 1, y - 3, R is a n - butyl radical, Z is oxygen, R 'and Re are

  alkyl radicals containing 1 to 8 carbon atoms,

  hydroxylated, R 'being able for example to be a

  methyl or ethyl radical and R "a hydroxyl radical

  ethyl. In another embodiment of the invention, there is used a complex of formula (II) in which x = 1, y = 3, Z is oxygen, R is a n-butyl radical and

GOLD',

O I, (III)

  Re / is a residue of tetrahydrofuran, dioxane or

morpholine.

  Examples of complexes that may be used in the context of the present invention include those which have the following chemical formulas: ## STR2 ## CH3 C2H5 2. n-C4H9-Sn-C13. O C4H 2 5

CH3

4. n-C4H9-Sn-Cl3. O0

C2H4OH

C2H CH 4. n.C H9 Sn-Cl O

4 9 3 2

X2H5 5. n-C4H9-Sn-C13. O

C2H4OH

CH3 6. n-C4H9-Sn-Cl3. O

C3H6OH

C2H5

7. n-C4H9-Sn-Cl3. OC0

C3H60H

C6H8 8. n-C4H9-Sn-Cl3. O

C3H6OH

CH-CH2

  9 n-C4H-Sn-C13 0 C2 9. n-C4 9 3 0 **** N *

CH -CH

2 2

CH- CH

  1 C. n-C4H9-Sn-Cl3. O NH 3 NH CHi-CH 2

CH, -CH,)

11. n-C4H9-Sn-C13. O -

CH2-CH2

/ C2H4OH

12. n-C4H9-Sn-Cl3. S

C2H4OH

  R 13. n -C4H9-Sn-Cl3. P-R '' R '' 'R' 14. n-C4H9-Sn-Cl3. N-R ''

R '

  The complexes used in the context of the present invention are easily prepared by reacting a tin halide or organotin, for example tin tetrachloride, dimethyldichlorotin, di-n-butyl-dichlorotin. , monobutyltrichloro-tin

  or monooctyltrichloro-tin with a complex of

mule R '//

Z (IV)

  I R "u R '' 'in which Z, R', Re and R '' 'have the meanings

indicated above.

  Thus, the complex 4 of the aforementioned formula can be obtained by bringing equimolar amounts of monobutyltrichloro-tin and ether together

  monomethyl ethylene glycol according to the reaction

  C4H9 - Sn - Cl3 + CH - O - C2H4OH

4 9 3 3 2.4

CH3 - C4H9 - SnCl3. O

C 2H 4 OH

  This reaction occurs spontaneously with

a strong release of heat.

  Similarly, complex 3 is obtained by reaction of monobutyltrichloro-tin with dibutyl ether, according to the following reaction: C4H9-Sn-Cl3 + C4H9-O-C4H9 / C4H9 C4H9-Sn-Cl3. O

C4H9

  Similarly, by taking equimolar amounts of monobutyltrichlorotin with ethylene glycol monoethyl ether, the desired complex is spontaneously obtained by the following reaction C4H9 SnCl3 + C2H5-O-C2H4-H

CH5

C4H9 SnCl3. o

C2H40H

  Similarly, we can obtain the

  complexes 9 and 10 by reacting a mole of mono-

  butyltrichloro-tin with respectively one mole of

dioxane or morpholine.

  The complexes used in accordance with the present invention may also be prepared by placing the starting materials in solution in a solvent such as benzene, toluene, xylene, dimethyl ether or dibutyl ether. When the solvent used is one of these ethers, a part of this ether

serves as a complexing agent.

  When the reaction is carried out in the absence

  a solvent, it is usually almost instantaneous.

  In the presence of a solvent, the reaction may have a

  duration up to about 30 minutes.

  0. TABLE I o r1 Time required o o Sary content for Temperature Behavior in aqueous phase - n Density OOil Tin product evaporate 10 g evaporation 2% 10% 30% 50% e kg / l O C

  i weight 150 SO'C max. ('C) H20 H20 H20 H20! '-

  (minutes) rX P Complex 3 28.79 1.25 11 163 1 2 2 2 C Complex 5 31.89 1, 5 8 175 1 1 1 I o <i-rt, W * O rt, Complex 9 32.06 1.55 15 183 1 3 3 3 tn 0 0O MBTCl 42.1 1.70 11 190 4/2 4/2 4/1 4/1 is product miscible with water 0 C 2 t phase separation 3 s product unstable 4s formation of unstable hydrates o '

See 0.

  The complexes used in the context of the present invention have been subjected to a laboratory test in an installation schematized in FIG.

drawing attached.

  In this plant, air was fed into a glass evaporator 2 at a rate of 30 liters per minute, after having been heated to 2000C in the heaters 3. In the evaporator 2, 10 g of

  product to be tested. The evaporator was equipped with a thermo-

  meter 4 marking a temperature of 130C. Evapo-

  2, the test products were sent to an untreated 5 pre-heated flask at 590 C. The contact time of the vapors of each product with the flask 5 a

been 5 seconds.

  Downstream of bottle 5, the vapors of the products

  were sucked into a hood 6.

  The thermal conditions remaining constant as well as the air flow and the evaporation surface, it is assumed that the steam flow of the products is funccion

only of their nature.

  The following Table II gives an account of

results of these tests.

TABLE II

  Product MBTC1 Complex Complex Complex

3 5 9

Time to evapo-

  ration for product g 11 11 8 15 in minutes CTU * at the point of contact with bottle 150. 145 160 130

Evaporation speed

  poration of product V in g / min 0.9 0.9 1.25 0.66 Yield factor

CTU * / V 167 161 128 197

% Sn 42.1 28.8 31.9 32

factor of

corrected CTU *

CTU * 397 559 401 616

  V x% Sn CTU * /% Sn 357 503 502 406 (*) CTU - thickness of the tin oxide layer expressed in Coating thickness Units measured a

  using Ame's Hot End Coating Meter

  The principle of measurement is based on the use of a light source in a test head which sends an oblique falsec onto a glass surface to be tested. Depending on the density of the glass surface, a part of the light is reflected on this surface and it can be recorded by a light diode which is also located in the test head. The contact between the test head and the glass surface is provided by a liquid having the same optical refractive index as the glass sample. Stannic oxide samples with a thicker surface density

  layer is known, serve to calibrate the team-

  is lying. Since the measurement process does not

  allows for an indirect determination of the thickness

  of the stannic oxide layer (by reflection

  of light) and that an exact calibration of the equipment

  depends on various other factors, we can not

  obtain only relative measurement values (CTU).

  Table II shows that the yield obtained with the complexes according to the invention is unexpectedly higher than that obtained with monobutyl trichloro tin (MBTCl), in spite of the lower tin content of the complexes. In addition, Table II also shows that despite a lower tin content than

  that of MBTC1, the complexes according to the invention

  almost as thick a layer of stannic oxide

only on the glass surface.

  Moreover, while to use monobutyl trichloro-tin, it is desirable to use a dry air atmosphere, if one wants to avoid the formation

  hydrates of this compound, the complexes according to

  invention can be used in an atmosphere

  of air whose moisture content is not con-

  because these complexes are insensitive to

  the humidity in much wider limits.

  It has also been found that, unlike

  monobutyltrichloro-tin, the complexes according to

  vention are much less corrosive vis-à-vis

  the equipment used and the skin of the users.

  Thus complexes 3 and 5 are half as corrosive as monobutyltrichloro-tin, while complex 9 is 1.4 times less corrosive than monobutyltrichloro-tin. As indicated above, the complexes of formula II can be used industrially in the vapor phase or in aqueous solution, the latter

  being sprayed on the glass surfaces to be treated.

  The aqueous solutions may contain about 15 to 50% by weight, preferably 30 to 40% by weight of at least

a complex of formula II.

  Industrial trials have revealed the consump-

  following complex configurations: - in the vapor phase: at 3 kg / 24 hours for the treatment of 100 to 300 vials per minute; in the liquid phase (aqueous solution sprayed): 2.5 to 10 kg / hour for the treatment of 100 to 300

bottles per minute.

  The process according to the invention can advantageously be carried out in the vapor phase in an installation such as that described in Belgian Patent BE 852,904, without it being however necessary to dehydrate the air serving as a carrier gas.

Claims (14)

  A process for the treatment of glass surfaces by treating these surfaces with a pyrolysable tin-containing composition, characterized in that a liquid composition or dissolved in a solvent is used, which contains at least one complex of formula R'I   RxSnCl Z! R "wherein x is an integer equal to 0 & 3, y is an integer of 1 to 4, with the proviso that x + y - 4, Z is oxygen, sulfur, phosphorus or oxygen. nitrogen, R is a straight or branched chain alkyl radical which may contain 1 to 8 carbon atoms or   a phenyl radical, R 'and R ", which can be identified as   different or different, designate an alkyl radical   If it is hydroxylated or phenylated or may form with Z a ring which may contain a hetero atom, and R '' 'which is unique and is present in the linear complex, 7 denotes phosphorus or nitrogen is a radical.   optionally hydroxylated alkyl or phenyl.   2. The process of claim 1, wherein   characterized in that a complex of formula (II) in which x 1, y = 3, Z is oxygen, R is n-butyl and R 'and R "are alkyl, optionally hydroxylated.   3. Process according to claim 2, characterized   in which a complex of formula (II) in which R 'is a methyl or ethyl radical and Ru is a hydroxyethyl radical.   4. Process according to claim 2, characterized   characterized in that a complex of formula (II) is used   wherein R 'and Ru are alkyl radicals containing 1 to 8 carbon atoms.   5. Process according to claim 2, characterized   in that a complex of formula (II) is used in which R ' 0) (III) \. R - '   means a residue of tetrahydrofuran, dioxane or morpholine.   6. The process of claim 1, wherein   characterized in that a complex of formula (II) in which x is 1, y is 3, Z is sulfur, R is n-butyl, R 'and R' are hydroxyethyl radicals.   7. Process according to any one of   preceding claims, characterized in that   uses the complex in the vapor phase.   8. Process according to any one of   Claims 1 to 6, characterized in that the   complex in the form of an aqueous solution containing & 50% by weight of complex.   9. A pyrolyzable composition intended to be sprayed on glass surfaces at temperatures above the pyrolysis temperature, characterized in that it comprises at least one liquid complex or dissolved in a solvent, corresponding to the formula R'i RxSnCly.Z (I), Rw Rw 'R' 'wherein x is an integer 0 A 3, y is an integer equal to i & 4, with the proviso that x + y - 4, Z is 1 oxygen, sulfur, phosphorus or nitrogen, R is an alkyl radical & straight or branched chain which may contain 1 to 8 carbon atoms or a phenyl radical, R 'and R ", which may be identical   or different, denote an alkyl radical   hydroxyl or phenyl, or can form with Z a ring which may contain a hetero atom, and R '' 'which is only present in the complex when Z designates   phosphorus or nitrogen is an alkyl radical hydroxylated or phenyl.   10. The composition according to claim 9, wherein it contains a complex of formula (II), wherein x = 1, y = 3, Z is oxygen, R is a n-butyl radical. and R 'and R "are   alkyl radicals, optionally hydroxylated or phenyl.   11. Composition according to claim 10,   characterized in that it contains a complex of   mule (II) in which R 'is a methyl radical or   ethyl and Rn is a hydroxyethyl radical.   12. The composition of claim 10   characterized in that it contains a complex of   mule (II) in which R 'and RI are radicals   alkyl containing 1 to 8 carbon atoms.   13. The composition of claim 10   characterized in that it contains a complex of mule (II) in which: R ' J) (III)   R "denotes a residue of tetrahydrofuran, dioxane or morpholine.   14. The composition of claim 9,   characterized in that it contains a complex of   mule (II) wherein x is 1, y is 3, Z is sulfur, R is n-butyl, R 'and R is   denote hydroxyethyl radicals.