CA2029716C - Glass bottles and process for preparing the same - Google Patents
Glass bottles and process for preparing the same Download PDFInfo
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- CA2029716C CA2029716C CA 2029716 CA2029716A CA2029716C CA 2029716 C CA2029716 C CA 2029716C CA 2029716 CA2029716 CA 2029716 CA 2029716 A CA2029716 A CA 2029716A CA 2029716 C CA2029716 C CA 2029716C
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- Prior art keywords
- coating
- bottle
- bottles
- glass
- glass bottle
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- 239000011521 glass Substances 0.000 title claims abstract description 60
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 114
- 239000011248 coating agent Substances 0.000 claims abstract description 108
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 38
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 21
- 238000007598 dipping method Methods 0.000 claims description 9
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 5
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 4
- 239000003513 alkali Substances 0.000 description 16
- 238000005507 spraying Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 235000013405 beer Nutrition 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 2
- 244000248349 Citrus limon Species 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005234 chemical deposition Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 235000016795 Cola Nutrition 0.000 description 1
- 235000011824 Cola pachycarpa Nutrition 0.000 description 1
- 239000004278 EU approved seasoning Substances 0.000 description 1
- 229910006853 SnOz Inorganic materials 0.000 description 1
- 235000013334 alcoholic beverage Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000006121 base glass Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 235000019992 sake Nutrition 0.000 description 1
- 235000013555 soy sauce Nutrition 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000011364 vaporized material Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 235000015041 whisky Nutrition 0.000 description 1
Landscapes
- Surface Treatment Of Glass (AREA)
Abstract
Disclosed is a process for preparing a coating for glass bottles, which comprises the step of bringing a glass bottle having an external surface temperature of 550 to 700°C into contact with a material which can form a coating comprising SnO2 or TiO2 so as to form a coating comprising SnO2 or TiO2 at a thickness of 400 to 1,000 angstroms.
Description
r ~7 GLASS BOTTLES AND PROCESS FOR PREPARING THE SAME
BACKGROUND OF THE INVENTION
1. Field of the Invention The present invention relates to glass bottles and lightweight glass bottles having a coating on the external surface thereof, particularly returnable bottles which can be recovered and used repeatedly, and a process for preparation thereof.
BACKGROUND OF THE INVENTION
1. Field of the Invention The present invention relates to glass bottles and lightweight glass bottles having a coating on the external surface thereof, particularly returnable bottles which can be recovered and used repeatedly, and a process for preparation thereof.
2. Description of the Related Art Hitherto, in the glass bottle industry, a surface of a one-way bottle was overcoated with an Sn02 or Ti02 coating during the process for preparing the bottle in order to improve the scuff resistance of the bottle surface.
More specifically, one-way bottles have on the external surface thereof a coating comprising Sn02 or Ti02 and formed by spraying SnCl4 or TiCl4 onto the bottles which have just been prepared and have not yet been annealed in an annealing chamber, remaining at a surface temperature of 400 to 550°C. Such process for coating is generally called hot end coating method.
The thickness of the coating thus formed is generally measured by a scale in "C.T.U." with a Hot End Coating Meter which is manufactured by American Glass Research Co. While the coating of one-way bottles in the art has a current standard of 20 to 80 C.T.U., the thickness of the coating is practically reduced to a range of 20 to 50 C.T.U. from the viewpoint of cost or appearance for avoiding the so-called iris phenomenon which may be caused by alkali washing before bottling.
The unit "C.T.U." herein means a merely optical unit used for process control and has no physical meaning.
However, 1 C.T.U. may be estimated at about 4 angstroms, and we have also confirmed the appropriateness of the value with Elipsometer Model AEP-100 (manufactured by Shimazu Co.). Therefore, the Sn02 or Ti02 coating of ~~~~.3 one-way bottles prepared by the hot end coating method may have a thickness of 300 angstroms or less.
Even though such a coating technique is effective as a method for affording physical properties such as abrasion resistance or lubricity to the one-way bottle, the method could not be applied to the returnable bottle because of the following reason.
The returnable bottle is recovered and used repeatedly in principle. Bottles recovered from the market are washed and sterilized every time on recovery with a high-concentration and hot alkali solution such as aqueous sodium hydroxide solution in washers in a bottling factory.
When the bottle having the coating formed by the method used for the one-way bottle is applied to such an alkali treatment, the coating will be easily peeled off and thus loses its effect. For instance, beer bottles are generally washed with a 4~ aqueous sodium hydroxide solution at a temperature of up to 80°C. Under such condition, the coating having a thickness of 20 to 50 C.T.U. formed by the method applied to the one-way bottle is usually peeled off in a single alkali washing cycle.
If the thickness of the coating is increased to a range of 50 to 80 C.T.U., the coating may not be completely peeled off in a single alkali washing cycle. Such a washing treatment, however, causes iris phenomenon on the surface of the bottle, and the bottle may lose its commercial value from the aesthetic standpoint of packaging. Therefore, even in the case of one-way bottle, to the bottle is applied a coating which can be easily peeled off in a single alkali washing cycle before bottling.
In some literature, the hot end coating method is carried out at a temperature in the range of 500 to 600°C. However, it can be scarcely supposed that the treatment would have been practically carried out at a temperature higher than about 550°C in view of the position where the hot end coating is carried out, i.e., before the annealing process, as well as for fear of deformation of the glass bottle due to such a high temperature. Another reason for the temperature limitation may be the temperature of the glass surface is measured by a primitive surface thermometer.
It has hitherto been impossible to prepare the returnable glass bottle having a coating which comprises SnOz or Ti02 as a main component and resists repeated alkali treatment.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide a novel process for preparing glass bottles having a coating which has resistance to repeated 1S alkali treatment.
It is a further object of the present invention to provide a novel process for preparing glass bottles having a coating which improves the strength of not only one-way bottles but returnable bottles.
It is yet another object of the present invention to provide a glass bottle having a coating which has resistance to repeated alkali treatment and improves the strength of the glass bottle.
Thus, the present invention provides, in its principal aspect, a process for preparing a coating f_-or glass bottles, which comprises the step of bringing a glass bottle having an external surface temperature of 550 to 700°C into contact with a material which can form a coating comprising Sn02 or Ti02 thereby to form a coating predominantly comprising Snot or Ti0? at a thickness of 900 to 1000 angstroms.
In another aspect, the present invention provides a glass bottle having on an external surface thereof a metal oxide coating predominantly comprising SnO~ or ,TiOz, the coating not being pee1ed off within E3 hours upon dipping into a 4$ by weight of an aqueous sodium hydroxide solution at 80°C.
More specifically, one-way bottles have on the external surface thereof a coating comprising Sn02 or Ti02 and formed by spraying SnCl4 or TiCl4 onto the bottles which have just been prepared and have not yet been annealed in an annealing chamber, remaining at a surface temperature of 400 to 550°C. Such process for coating is generally called hot end coating method.
The thickness of the coating thus formed is generally measured by a scale in "C.T.U." with a Hot End Coating Meter which is manufactured by American Glass Research Co. While the coating of one-way bottles in the art has a current standard of 20 to 80 C.T.U., the thickness of the coating is practically reduced to a range of 20 to 50 C.T.U. from the viewpoint of cost or appearance for avoiding the so-called iris phenomenon which may be caused by alkali washing before bottling.
The unit "C.T.U." herein means a merely optical unit used for process control and has no physical meaning.
However, 1 C.T.U. may be estimated at about 4 angstroms, and we have also confirmed the appropriateness of the value with Elipsometer Model AEP-100 (manufactured by Shimazu Co.). Therefore, the Sn02 or Ti02 coating of ~~~~.3 one-way bottles prepared by the hot end coating method may have a thickness of 300 angstroms or less.
Even though such a coating technique is effective as a method for affording physical properties such as abrasion resistance or lubricity to the one-way bottle, the method could not be applied to the returnable bottle because of the following reason.
The returnable bottle is recovered and used repeatedly in principle. Bottles recovered from the market are washed and sterilized every time on recovery with a high-concentration and hot alkali solution such as aqueous sodium hydroxide solution in washers in a bottling factory.
When the bottle having the coating formed by the method used for the one-way bottle is applied to such an alkali treatment, the coating will be easily peeled off and thus loses its effect. For instance, beer bottles are generally washed with a 4~ aqueous sodium hydroxide solution at a temperature of up to 80°C. Under such condition, the coating having a thickness of 20 to 50 C.T.U. formed by the method applied to the one-way bottle is usually peeled off in a single alkali washing cycle.
If the thickness of the coating is increased to a range of 50 to 80 C.T.U., the coating may not be completely peeled off in a single alkali washing cycle. Such a washing treatment, however, causes iris phenomenon on the surface of the bottle, and the bottle may lose its commercial value from the aesthetic standpoint of packaging. Therefore, even in the case of one-way bottle, to the bottle is applied a coating which can be easily peeled off in a single alkali washing cycle before bottling.
In some literature, the hot end coating method is carried out at a temperature in the range of 500 to 600°C. However, it can be scarcely supposed that the treatment would have been practically carried out at a temperature higher than about 550°C in view of the position where the hot end coating is carried out, i.e., before the annealing process, as well as for fear of deformation of the glass bottle due to such a high temperature. Another reason for the temperature limitation may be the temperature of the glass surface is measured by a primitive surface thermometer.
It has hitherto been impossible to prepare the returnable glass bottle having a coating which comprises SnOz or Ti02 as a main component and resists repeated alkali treatment.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide a novel process for preparing glass bottles having a coating which has resistance to repeated 1S alkali treatment.
It is a further object of the present invention to provide a novel process for preparing glass bottles having a coating which improves the strength of not only one-way bottles but returnable bottles.
It is yet another object of the present invention to provide a glass bottle having a coating which has resistance to repeated alkali treatment and improves the strength of the glass bottle.
Thus, the present invention provides, in its principal aspect, a process for preparing a coating f_-or glass bottles, which comprises the step of bringing a glass bottle having an external surface temperature of 550 to 700°C into contact with a material which can form a coating comprising Sn02 or Ti02 thereby to form a coating predominantly comprising Snot or Ti0? at a thickness of 900 to 1000 angstroms.
In another aspect, the present invention provides a glass bottle having on an external surface thereof a metal oxide coating predominantly comprising SnO~ or ,TiOz, the coating not being pee1ed off within E3 hours upon dipping into a 4$ by weight of an aqueous sodium hydroxide solution at 80°C.
~'dC~~~~;"~~n ~d ~~9 d~ ~°
The glass bottle having the coating according to the present invention is excellent in resistance to abrasion and resistance to alkali and can be used repeatedly as a returnable glass bottle.
Further, the strength of the glass bottle having the coating according to the present invention can be improved, so that the weight of the glass bottle can be reduced.
Still further, the coating has a comparatively large refractive index and thus the reflection of light on the glass surface may increase, so that the discoloration of a content or other troubles can be prevented.
Particularly, when the content is beer, the so-called "sun-struck" flavour which may be caused by the invasion of light can be suppressed.
BRIEF DESCRIPTION OF THE DRAWINGS
Figures 1 and 2 are graphs which show the relationship between the surface temperature of a glass bottle and the time required for peeling the coating, respectively;
Figures 3 and 4 are graphs which show the relationship between the thickness of the coating and the time required for peeling the coating, respectively;
Figure 5 is~a graph which shows the relationship between the internal pressure strength of bottles and the frequency of passing the bottle through a bottling step including an alkali washing;
Figure 6 is a graph which shows the relationship between the impact strength of bottles and the frequency of passing the bottle through a bottling step including an alkali washing;
Figure 7 is a photomicrograph of the surface of the coating comprising Sn02 according to the present invention at a thickness of 600 angstroms after dipping into 4~ by weight aqueous sodium hydroxide solution (2,000 x magnification); and ~ ~~ ' $ ~~ ~~
~:.~ ~~~ a Figure 8 is a photomicrograph of the surface of the coating comprising Sn02 according to the hot end coating method at a thickness of 600 angstroms after dipping into 4% by weight aqueous sodium hydroxide solution (2,000 x magnification).
DESCRIPTION OF THE PREFERRED EMBODIMENT
Glass Bottle A glass bottle to which the present invention can be applied, i.e., a glass bottle as a base is a returnable glass bottle which is used repeatedly. Such a returnable glass bottle includes glass bottles for alcoholic drinks such as beer, whiskey or sake, seasonings such as soy sauce or vinegar, refreshing drinks such as cola, lemon pop or juice, milk or the like.
Glass bottles which can enjoy the effect of the present invention include returnable bottles for liquid carbonate drinks such as beer, cola or lemon pop in which carbonate gas is dissolved to an internal pressure of 1.0 to 4.0 kg/cm2, preferably 1.2 to 2.5 kg/cm2 at room temperature.
The returnable glass bottles may include glass bottles comprising soda lime glass or borosilicate glass, preferably soda lime glass.
Preparation of Coating (1) -Coating Conditions The process for preparing the coating of the present invention comprises the step of bringing a glass bottle having a specific external surface temperature into contact with a material which can form a coating comprising Sn02 or Ti02 so as to form a coating comprising Sn02 or Ti02 as the main component.
The process for preparing a coating of the present invention requires an external surface temperature of the glass bottle at 550 to 700°C, preferably higher than 600°C in the case of the coating predominantly comprising Sn02 and higher than 630°C in the case of the coating predominantly comprising Ti02. If the external surface ~, ~,;
temperature of the glass bottle is less than 550°C, the coating is inevitably peeled off within 8 hours upon dipping the bottle into a 4~ by weight aqueous sodium hydroxide solution at 80°C even if the coating has a thickness in the range of 400 to 1,000 angstroms, which is the same range of the present invention. It is not preferable that the bottle thus treated has iris phenomenon. The temperature exceeding 700°C is undesirable because the glass bottle tends to be deformed by such a high temperature and .to be cracked due to the difference of coefficients of thermal expansion between the bottle and the coating.
Further, according to the process of the present invention, the coating comprising Sn02 or Ti02 as the main component must be prepared at a thickness of 400 to 1,000 angstroms under the above temperature condition.
The coating having a thickness of less than 400 angstroms is not preferred because it has a poor durability and is inevitably peeled off ..within 3 hours upon dipping into a 4~ by weight aqueous sodium hydroxide solution at 80°C.
The coating having a thickness exceeding 1,000 angstroms is not preferred either because it causes interference phenomenon which impairs the aesthetic appearance of the bottle and because it tends to be cracked due to the difference of coefficients of thermal expansion between the bottle and the coating.
(2) Material for Forming the Coating In the process for preparing the coating according to the present invention, a coating comprising Sn02 or Ti02 as the main component is prepared on the glass bottle having a specific external surface temperature.
As a material which can form the coating comprising Sn02 or Ti02, any material which produces Sn02 or Ti02 upon pyrolysis can be used. For example, the material includes SnClQ, TiCl4, organometallic compounds of Sn or Ti such as (CH3)2SnC12, metal alcolates and the like.
The glass bottle having the coating according to the present invention is excellent in resistance to abrasion and resistance to alkali and can be used repeatedly as a returnable glass bottle.
Further, the strength of the glass bottle having the coating according to the present invention can be improved, so that the weight of the glass bottle can be reduced.
Still further, the coating has a comparatively large refractive index and thus the reflection of light on the glass surface may increase, so that the discoloration of a content or other troubles can be prevented.
Particularly, when the content is beer, the so-called "sun-struck" flavour which may be caused by the invasion of light can be suppressed.
BRIEF DESCRIPTION OF THE DRAWINGS
Figures 1 and 2 are graphs which show the relationship between the surface temperature of a glass bottle and the time required for peeling the coating, respectively;
Figures 3 and 4 are graphs which show the relationship between the thickness of the coating and the time required for peeling the coating, respectively;
Figure 5 is~a graph which shows the relationship between the internal pressure strength of bottles and the frequency of passing the bottle through a bottling step including an alkali washing;
Figure 6 is a graph which shows the relationship between the impact strength of bottles and the frequency of passing the bottle through a bottling step including an alkali washing;
Figure 7 is a photomicrograph of the surface of the coating comprising Sn02 according to the present invention at a thickness of 600 angstroms after dipping into 4~ by weight aqueous sodium hydroxide solution (2,000 x magnification); and ~ ~~ ' $ ~~ ~~
~:.~ ~~~ a Figure 8 is a photomicrograph of the surface of the coating comprising Sn02 according to the hot end coating method at a thickness of 600 angstroms after dipping into 4% by weight aqueous sodium hydroxide solution (2,000 x magnification).
DESCRIPTION OF THE PREFERRED EMBODIMENT
Glass Bottle A glass bottle to which the present invention can be applied, i.e., a glass bottle as a base is a returnable glass bottle which is used repeatedly. Such a returnable glass bottle includes glass bottles for alcoholic drinks such as beer, whiskey or sake, seasonings such as soy sauce or vinegar, refreshing drinks such as cola, lemon pop or juice, milk or the like.
Glass bottles which can enjoy the effect of the present invention include returnable bottles for liquid carbonate drinks such as beer, cola or lemon pop in which carbonate gas is dissolved to an internal pressure of 1.0 to 4.0 kg/cm2, preferably 1.2 to 2.5 kg/cm2 at room temperature.
The returnable glass bottles may include glass bottles comprising soda lime glass or borosilicate glass, preferably soda lime glass.
Preparation of Coating (1) -Coating Conditions The process for preparing the coating of the present invention comprises the step of bringing a glass bottle having a specific external surface temperature into contact with a material which can form a coating comprising Sn02 or Ti02 so as to form a coating comprising Sn02 or Ti02 as the main component.
The process for preparing a coating of the present invention requires an external surface temperature of the glass bottle at 550 to 700°C, preferably higher than 600°C in the case of the coating predominantly comprising Sn02 and higher than 630°C in the case of the coating predominantly comprising Ti02. If the external surface ~, ~,;
temperature of the glass bottle is less than 550°C, the coating is inevitably peeled off within 8 hours upon dipping the bottle into a 4~ by weight aqueous sodium hydroxide solution at 80°C even if the coating has a thickness in the range of 400 to 1,000 angstroms, which is the same range of the present invention. It is not preferable that the bottle thus treated has iris phenomenon. The temperature exceeding 700°C is undesirable because the glass bottle tends to be deformed by such a high temperature and .to be cracked due to the difference of coefficients of thermal expansion between the bottle and the coating.
Further, according to the process of the present invention, the coating comprising Sn02 or Ti02 as the main component must be prepared at a thickness of 400 to 1,000 angstroms under the above temperature condition.
The coating having a thickness of less than 400 angstroms is not preferred because it has a poor durability and is inevitably peeled off ..within 3 hours upon dipping into a 4~ by weight aqueous sodium hydroxide solution at 80°C.
The coating having a thickness exceeding 1,000 angstroms is not preferred either because it causes interference phenomenon which impairs the aesthetic appearance of the bottle and because it tends to be cracked due to the difference of coefficients of thermal expansion between the bottle and the coating.
(2) Material for Forming the Coating In the process for preparing the coating according to the present invention, a coating comprising Sn02 or Ti02 as the main component is prepared on the glass bottle having a specific external surface temperature.
As a material which can form the coating comprising Sn02 or Ti02, any material which produces Sn02 or Ti02 upon pyrolysis can be used. For example, the material includes SnClQ, TiCl4, organometallic compounds of Sn or Ti such as (CH3)2SnC12, metal alcolates and the like.
~ ~' It is also possible to improve the properties of the coating by incorporating other metal oxides or the like within the scope of the purpose of the present invention.
(3) Preparation of the Coating In the process for preparing the coating according to the present invention, the glass bottle having a specific external surface temperature and the material for forming the coating can be contacted by any method without limitation with the proviso that the method can perform the formulation of the coating on the surface of the glass bottle. The coating can be formed-by the methods such as chemical deposition or spraying method.
The chemical deposition method indicates a method for preparing a coating of Sn02 or Ti02 on the external surface of the bottle comprising the steps of vaporizing the above-mentioned material by heating, transferring the vaporized material into a coating chamber by means of a dry gas such as air, oxygen or an inert gas, and reacting the material with oxygen or water which exists in the atmosphere or on the surface of the bottle. The spraying method refers to a method comprising the steps of dissolving the material in an organic solvent, spraying it on the surface of the bottle, and pyrolytically decomposing it to form the coating.
Coating The glass bottle having the coating according to the present invention generally exhibits a silvery white appearance. It forms a contrast with the fact that the appearance of the glass bottle having the coating according to the hot end coating method is the same appearance of an uncoated glass bottle.
The coating obtained by the process according to the present invention is supposed to be attached securely by the so-called "anchor effect" which is caused by the transfer of the coating component to the glass phase of the bottle to some degree. As a result, it is supposed that the coating hardly peels off even in the case of an 6~ ,b~F s°~ ~~ ~ ~ 'a Ea! ~i' iaJ R3a g n ~;.
alkali treatment at a high temperature and a high concentration. We have confirmed the following fact. It was observed by a microscope (2,000 x magnification) that peeled portions on the surface of the coating comprising Sn02 at a thickness of 600 angstroms according to the present invention formed like dots upon dipping into a 4~
by weight aqueous sodium hydroxide solution. On the other hand, it was observed by a microscope (2,000 x magnification) that peeled portions on the surface of the coating comprising Sn02 at a thickness of 600 angstroms according to the hot end coating method spread continuously over almost all the surface after the alkali treatment as mentioned above.
The coating obtained by the present invention has an indication that the coating is not peeled off within 8 hours upon dipping into a 4~ by weight aqueous sodium hydroxide solution at 80°C. The wording "the coating is not peeled off within 8 hours" means that no peeling of the coating is visually observed after the above alkali treatment.
Lightweight Glass Bottle The glass bottle having the coating according to the present invention can be improved in strength. In particular, the impact strength and the internal pressure resistance can be improved. As a result, it is possible for the bottle having the coating of the present invention to possess a strength equal to or higher than that of an untreated glass bottle, even if the base glass bottle has a thin glass thickness. In other words, the process for preparing the coating according to the present invention enables the preparation of a reduced weight glass bottle, i.e., a lightweight glass bottle.
The following examples are provided to enable one skilled in the art to practice the present invention.
However, these examples are merely illustrative of the invention and are not to be read as limiting the scope of the invention.
(3) Preparation of the Coating In the process for preparing the coating according to the present invention, the glass bottle having a specific external surface temperature and the material for forming the coating can be contacted by any method without limitation with the proviso that the method can perform the formulation of the coating on the surface of the glass bottle. The coating can be formed-by the methods such as chemical deposition or spraying method.
The chemical deposition method indicates a method for preparing a coating of Sn02 or Ti02 on the external surface of the bottle comprising the steps of vaporizing the above-mentioned material by heating, transferring the vaporized material into a coating chamber by means of a dry gas such as air, oxygen or an inert gas, and reacting the material with oxygen or water which exists in the atmosphere or on the surface of the bottle. The spraying method refers to a method comprising the steps of dissolving the material in an organic solvent, spraying it on the surface of the bottle, and pyrolytically decomposing it to form the coating.
Coating The glass bottle having the coating according to the present invention generally exhibits a silvery white appearance. It forms a contrast with the fact that the appearance of the glass bottle having the coating according to the hot end coating method is the same appearance of an uncoated glass bottle.
The coating obtained by the process according to the present invention is supposed to be attached securely by the so-called "anchor effect" which is caused by the transfer of the coating component to the glass phase of the bottle to some degree. As a result, it is supposed that the coating hardly peels off even in the case of an 6~ ,b~F s°~ ~~ ~ ~ 'a Ea! ~i' iaJ R3a g n ~;.
alkali treatment at a high temperature and a high concentration. We have confirmed the following fact. It was observed by a microscope (2,000 x magnification) that peeled portions on the surface of the coating comprising Sn02 at a thickness of 600 angstroms according to the present invention formed like dots upon dipping into a 4~
by weight aqueous sodium hydroxide solution. On the other hand, it was observed by a microscope (2,000 x magnification) that peeled portions on the surface of the coating comprising Sn02 at a thickness of 600 angstroms according to the hot end coating method spread continuously over almost all the surface after the alkali treatment as mentioned above.
The coating obtained by the present invention has an indication that the coating is not peeled off within 8 hours upon dipping into a 4~ by weight aqueous sodium hydroxide solution at 80°C. The wording "the coating is not peeled off within 8 hours" means that no peeling of the coating is visually observed after the above alkali treatment.
Lightweight Glass Bottle The glass bottle having the coating according to the present invention can be improved in strength. In particular, the impact strength and the internal pressure resistance can be improved. As a result, it is possible for the bottle having the coating of the present invention to possess a strength equal to or higher than that of an untreated glass bottle, even if the base glass bottle has a thin glass thickness. In other words, the process for preparing the coating according to the present invention enables the preparation of a reduced weight glass bottle, i.e., a lightweight glass bottle.
The following examples are provided to enable one skilled in the art to practice the present invention.
However, these examples are merely illustrative of the invention and are not to be read as limiting the scope of the invention.
~'~~ ;~> ~ ~ , ~~a a ., ..aF
Example 1 A coating comprising Sn02 or Ti02 as the main component was formed at a thickness of 600 angstroms on large-size beer bottles (manufactured by Kirin Beer K.K., returnable bottles having a weight of 605 g prepared in a bottle making machine) at various surface temperatures of the glass bottles. The bottles thus obtained were dipped into a 4~ by weight aqueous sodium hydroxide solution at 80°C, and the time required for the peeling of the coating was measured. The results are shown in Figures 1 and 2.
Example 2 A coating comprising Sn02 or Ti02 as the main component was formed on the same bottles as in Example 1 at various thicknesses at a glass surface temperature of 630°C. The bottles thus obtained were treated in the same manner as in Example 1, and the time required for the peeling of the coating was measured. The results are shown in Figures 3 and 4.
Example 3 and Comparative Example 1 The same large-size bottles as in Example 1 and lightweight large-size bottles which had the same profile as the above large-size bottle but had their weight reduced by 130 g were provided.
While the external surface temperature of these bottles was maintained at 600 to 700°C over the entire surface thereof, an Sn02 coating was formed by spraying SnCl4 and depositing it on the surface of the bottles at an average coating thickness of 600 angstroms. The bottles having the coating thus obtained and uncoated bottles having a weight of 605 g were passed 30 times repeatedly through a bottling step in an ordinary beer factory including an alkali washing (with a 4~ by weight aqueous sodium hydroxide solution at a maximum temperature of 80°C for about 10 minutes).
These bottles which had been subjected to the above test were then estimated for the internal pressure ~;~~ ~ ~°
resistance and the impact strength. The results are shown in Figures 5 and 6. Comparing the uncoated bottles having a weight of 605 g with the coated bottle having a weight of 605 g, the reduction of the strength of the coated bottle is lesser than that of the uncoated bottle.
The coated bottle having a weight of 475 g has the same internal pressure resistance as the 605 g uncoated bottles. Further, the 475 g coated bottle is superior in impact strength to the 605 g uncoated bottle. The results show the fact that. the weight of glass bottles can be reduced by the coating according to the present invention.
Ten (10) bottles of each group after passing through the above bottling step were picked up to estimate the damage by the scuff marks on the bottles. The results are shown in Table 1.
Table 1 605 g Coated +1 +1 +1 +1 +1 +1 +1 +1 +1 +1 475 g Coated +1 +1 +1 +1 +1 +1 +1 +1 +1 +1 605 g Uncoated +4 +4 +4 +4 +4 +4 +4 +4 +4 +4 Indices to the damage of the samples are as follows.
0 : Intact +1: Slightly damaged +2: Damaged +3: Considerably damaged +4: Severely damaged Comparative Example 2 An Sn02 coating was formed at a thickness of 160 angstroms (about 40 C.T.U.) by spraying SnCl4 onto the same bottles having a weight of 605 g as in Example 3 at a surface temperature of 400 to 500°C.
The glass bottles thus obtained were passed through the same bottling step as in Example 3. As a result, the coating was completely peeled off by one passing.
Example 1 A coating comprising Sn02 or Ti02 as the main component was formed at a thickness of 600 angstroms on large-size beer bottles (manufactured by Kirin Beer K.K., returnable bottles having a weight of 605 g prepared in a bottle making machine) at various surface temperatures of the glass bottles. The bottles thus obtained were dipped into a 4~ by weight aqueous sodium hydroxide solution at 80°C, and the time required for the peeling of the coating was measured. The results are shown in Figures 1 and 2.
Example 2 A coating comprising Sn02 or Ti02 as the main component was formed on the same bottles as in Example 1 at various thicknesses at a glass surface temperature of 630°C. The bottles thus obtained were treated in the same manner as in Example 1, and the time required for the peeling of the coating was measured. The results are shown in Figures 3 and 4.
Example 3 and Comparative Example 1 The same large-size bottles as in Example 1 and lightweight large-size bottles which had the same profile as the above large-size bottle but had their weight reduced by 130 g were provided.
While the external surface temperature of these bottles was maintained at 600 to 700°C over the entire surface thereof, an Sn02 coating was formed by spraying SnCl4 and depositing it on the surface of the bottles at an average coating thickness of 600 angstroms. The bottles having the coating thus obtained and uncoated bottles having a weight of 605 g were passed 30 times repeatedly through a bottling step in an ordinary beer factory including an alkali washing (with a 4~ by weight aqueous sodium hydroxide solution at a maximum temperature of 80°C for about 10 minutes).
These bottles which had been subjected to the above test were then estimated for the internal pressure ~;~~ ~ ~°
resistance and the impact strength. The results are shown in Figures 5 and 6. Comparing the uncoated bottles having a weight of 605 g with the coated bottle having a weight of 605 g, the reduction of the strength of the coated bottle is lesser than that of the uncoated bottle.
The coated bottle having a weight of 475 g has the same internal pressure resistance as the 605 g uncoated bottles. Further, the 475 g coated bottle is superior in impact strength to the 605 g uncoated bottle. The results show the fact that. the weight of glass bottles can be reduced by the coating according to the present invention.
Ten (10) bottles of each group after passing through the above bottling step were picked up to estimate the damage by the scuff marks on the bottles. The results are shown in Table 1.
Table 1 605 g Coated +1 +1 +1 +1 +1 +1 +1 +1 +1 +1 475 g Coated +1 +1 +1 +1 +1 +1 +1 +1 +1 +1 605 g Uncoated +4 +4 +4 +4 +4 +4 +4 +4 +4 +4 Indices to the damage of the samples are as follows.
0 : Intact +1: Slightly damaged +2: Damaged +3: Considerably damaged +4: Severely damaged Comparative Example 2 An Sn02 coating was formed at a thickness of 160 angstroms (about 40 C.T.U.) by spraying SnCl4 onto the same bottles having a weight of 605 g as in Example 3 at a surface temperature of 400 to 500°C.
The glass bottles thus obtained were passed through the same bottling step as in Example 3. As a result, the coating was completely peeled off by one passing.
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Example 4 The formation of a coating was carried out in the same manner as in Example 3 except that a Ti02 coating was formed by spraying TiCl4 onto the same bottles having a weight of 605 g as in Example 3.
The glass bottles thus obtained were passed 15 times repeatedly through the same bottling step as in Example 3. The results were as good as those in Example 3.
Comparative Example 3 A coating was formed in the same manner as in Comparative Example 2 except that a Ti02 coating was formed by spraying TiCl4.
The glass bottles thus obtained were passed through the same bottling step as in Example 3. As a result, the coating was completely peeled off by one passing.
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Example 4 The formation of a coating was carried out in the same manner as in Example 3 except that a Ti02 coating was formed by spraying TiCl4 onto the same bottles having a weight of 605 g as in Example 3.
The glass bottles thus obtained were passed 15 times repeatedly through the same bottling step as in Example 3. The results were as good as those in Example 3.
Comparative Example 3 A coating was formed in the same manner as in Comparative Example 2 except that a Ti02 coating was formed by spraying TiCl4.
The glass bottles thus obtained were passed through the same bottling step as in Example 3. As a result, the coating was completely peeled off by one passing.
Claims (8)
1. A process for preparing a coating for a glass bottle, which comprises the step of contacting a material which can form a coating comprising SnO2 or TiO2 with the glass bottle which has been heated to have an external surface temperature of 600 to 700°C when the material can form a coating comprising SnO2 or of 630 to 700°C when the material can form a coating comprising TiO2, thereby to form a coating predominantly comprising SnO2 or TiO2 at a thickness of 400 to 1,000 angstroms, the coating not being peeled off within 8 hours upon dipping into 4% by weight of an aqueous sodium hydroxide solution at 80°C.
2. A process for preparing a lightweight glass bottle, which comprises the step of contacting a material which can form a coating comprising SnO2 or TiO2 with the glass bottle which has been heated to have an external surface temperature of 600 to 700°C when the material can form a coating comprising SnO2 or of 630 to 700°C when the material can form a coating comprising TiO2, thereby to form a coating predominantly comprising SnO2 or TiO2 at a thickness of 400 to 1,000 angstroms, the coating slot being peeled off within 8 hours upon dipping into 4% by weight of an aqueous sodium hydroxide solution at 80°C.
3. A process according to claim 1 or 2, wherein the material can form a coating comprising SnO2.
4. A process according to claim 3, wherein the material is SnCl4.
5. A process according to claim 1 or 2, wherein the material can form a coating comprising TiO2.
6. A process according to claim 5, wherein the material is TiCl4.
7. A glass bottle made by the process according to claim 1.
8. A glass bottle made by the process according to claim 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2029716 CA2029716C (en) | 1990-11-09 | 1990-11-09 | Glass bottles and process for preparing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2029716 CA2029716C (en) | 1990-11-09 | 1990-11-09 | Glass bottles and process for preparing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2029716A1 CA2029716A1 (en) | 1992-05-10 |
| CA2029716C true CA2029716C (en) | 2002-01-29 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2029716 Expired - Fee Related CA2029716C (en) | 1990-11-09 | 1990-11-09 | Glass bottles and process for preparing the same |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2029716C (en) |
-
1990
- 1990-11-09 CA CA 2029716 patent/CA2029716C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CA2029716A1 (en) | 1992-05-10 |
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