CN1113075A - Brittle oxide substrates strengthened by cross-linkable silanes - Google Patents
Brittle oxide substrates strengthened by cross-linkable silanes Download PDFInfo
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- CN1113075A CN1113075A CN94190546A CN94190546A CN1113075A CN 1113075 A CN1113075 A CN 1113075A CN 94190546 A CN94190546 A CN 94190546A CN 94190546 A CN94190546 A CN 94190546A CN 1113075 A CN1113075 A CN 1113075A
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- silane
- brittle oxide
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- oxide substrate
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
- Paints Or Removers (AREA)
- Details Of Rigid Or Semi-Rigid Containers (AREA)
- Sampling And Sample Adjustment (AREA)
- Liquid Crystal (AREA)
- Inorganic Insulating Materials (AREA)
- Silicon Polymers (AREA)
Abstract
A method is described for strengthening or restoring strength to a brittle oxide substrate which includes the steps of coating the brittle oxide substrate with an aqueous solution containing a silane-based composition, and curing the coating to form a transparent layer on the brittle oxide substrate. Also disclosed are novel compositions used to coat brittle oxide substrates, and silane-coated brittle oxide containers.
Description
The present invention relates to a kind of method that strengthens the brittle oxide substrate, also relate to the aqueous solution that contains based on the composition of silane, and relate to the substrate of the brittle oxide that is aggregated crosslinked silicone coating, more particularly, the present invention relates to a kind of glass container that makes and strengthen, promptly recover the method for the container of the method for intensity of glass container and the polymerization crosslinking silicone coating that obtains thus.
Such as some actual shown mechanical performances of the fragile material of substrate of glass, as tensile strength, general than theoretical predicted littler, this is that the body of the goods imperfect or that make with this material owing to the structure of test specimen is interior or surperficially have a spot of impurity to cause.Be to adopt progressively zone melting in the past to improve crystal structure and, to attempt to improve the mechanical performance of fragile material from the floating decontamination of the brittle substance of fusion.For nonmetal fragile material, but also adopted the sandwich construction that constitutes by brittle substance to improve its mechanical performance.In addition, adopted the surface treatment of fragile material again, prevented that its surface from fraying, and can play some effect for supporting fragile material.
Glass is a class of the material that intensity is the highest known to the people with regard to its essence.In theory, the silicate glass of standard should be able to bear the application up to 140 to 20,000,000,000 Bath cards (200 ten thousand to 300 ten thousand pounds per square inch).Yet in fact, generally the intensity that can reach only is this card of 70 megabars, promptly 10, and 000psi.
To inconsistent explanation between predicted value and the measured value is to exist blemish or crackle.These defectives play a part fracture basically to the skeleton siloxane network (Si-O-Si) of glass.And this damage of siloxane network plays a part to make and applies external force and concentrate, and far below desired stress (if having defective to play the words that stress is concentrated effect) the final damage is being taken place down until glassware.Though be for glass here, this same theory is also applicable to any fragile material that did not present remarkable plastic deformation before damaging.
For example, in the situation of glass container, the defective on surface may be from multiple source, from unfused furnace charge to the scratch that is produced when slipping at rigid surface (comprising other glassware).For example, make in the tankage typical, glassware one forms from them, all possible major injury of various processing they.Contact with airborne particulate and moisture, contact, all can cause vessel strength to reduce widely because of producing defective with other bottle, guide rail and other treatment facility and the conveyer belt that transports them.
Some researchers alleviate the problem that the glass actual strength exists in the method for seeking for a long time.To the strength-enhanced that many improvement caused that is shaped and processing method is done is not satisfied, still unavoidably stays defective from the teeth outwards because these improve.For this reason, researcher's target is at how to reduce these defect influence on object after defective produces inevitably.
The certain methods of improving strength of glass comprises people's such as Aratani patent U.S.4,859,636, wherein, the metal ion in the glass by the replacement of larger-diameter ion to produce surface pressing.People's such as Poole U.S.3,743,491 also relate to the way that adopts bearing stress, but also have been to use polymer coating to protect its surface not to be subjected to further wearing and tearing.
People's such as Hashimoto U.S.4 handles glass surface with silane coupling agent for 891,241, with the polymer overmold that contains acryloyl group and/or methacrylyl, makes the molecule aggregation that contains these groups by irradiation or heat treatment then then.' 241 patents also further show to have only silane can not play humidification to substrate, and acrylate is requisite in any enhancing.
Though, above-mentioned patent, they all make the glass intensity through certain processing improve to some extent separately, however they are not impeccable.It is longer that the time ratio that some processing takies can provide in manufacture process, thereby need off-line operation.Also also have some to relate to safety of workers and healthy problem.Particularly, using and handling of organic solvent and acrylate and methacrylate (methacrylate) compound is that the producer will be concerned about.
Therefore, need a kind of intensity of brittle oxide substrate that can make to increase to some extent, the method for the enhancing brittle oxide substrate that can manage to address the above problem does not again so still have this method.And, for compare brittle oxide substrate with the brittle oxide substrate of uncoated, demand is arranged also through applying with obvious improvement intensity.
Further be yet to need to make oxide base to have the method for the enhancing brittle oxide substrate of acceptable mark and/or moisture-proof.
In addition, be that the transparent brittle oxide substrate with the polymerization crosslinking silicone coating also exists demand to applicator.
Other purpose of the present invention and advantage will partly be introduced in the following description, and some then may be obvious that from specification, or can learn from practice of the present invention.Some main points and combination thereof by specifically noting in appended claims just can realize objects and advantages of the present invention.
In order to realize purpose of the present invention, according to broadly described those targets, the present invention relates to a kind of method of the enhancing brittle oxide substrate that comprises the following steps.Be the aqueous solution of based composition and use thereof in packaging at first, apply the brittle oxide substrate with containing with silane.Contain with silane is that the aqueous solution of based composition and use thereof in packaging does not have organic solvent basically.Further be to be that the composition of base has following formula after the hydrolysis with silane in the aqueous solution:
(OH)
3SiR " R " is an organo-functional group.What will contain hydrolysis is after the aqueous solution of based composition and use thereof in packaging is coated in the brittle oxide substrate, this coat to be cured with silane, makes it form the layer of transparent layer in the brittle oxide substrate.In composition based on silane, R " selection the intensity of the brittle oxide substrate before (i) and the coating step is compared; the intensity with brittle oxide substrate of cured coated layer should have improvement is obviously arranged, and (ii) the coat of Gu Huaing can not influence the mark of brittle oxide substrate.
The present invention yet relates to a kind of method similar to the above, that different is R " the make sure intensity of the brittle oxide substrate before (i) and the coating step of selection compare; the intensity of substrate with brittle oxide of cured coated layer should have obvious improvement, (ii) since in the brittle oxide substrate cured coated layer and the intensity improved significantly should keep the moisture-proof at least about 50%.
The invention still further relates to a kind of brittle oxide container of polymerization crosslinking silicone coating.Concrete is, the brittle oxide container of polymerization crosslinking silicone coating, and it comprises a brittle oxide container and the hyaline layer that solidifies last layer polymerization crosslinking siloxanes on the brittle oxide container outer surface preferably.The polymerization crosslinking siloxanes is formed by the composition based on silane of organic solvent-free existence hydrolysis in the aqueous solution and basic.The composition based on silane of hydrolysis, for example.Can be to be selected from by methacryloxypropyl trimethoxy silane (MPTMO), glycidoxypropyl trimethoxy silane (GPTMO), vinyltrimethoxy silane (VTMO), 2-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane (CETMO), MTMS (MTMO), 3,3-dimethoxy propyl trimethoxy silicane (DPTMO), 5,6-epoxy radicals hexyl trimethoxy silane (EHTMO), N-(trimethoxy-silylpropyl)-maleic amide, 3-urea groups propyl trimethoxy silicane (UPTMO), 1, two (trimethoxysilyl) ethane (BTMOE) of 2-, 1, two (the 3-trimethoxysilyl propoxyl group) ethane (BTMOPE) of 2-, their hydrolysed form with and composition thereof the group formed.
The invention further relates to novel composition, include, but not limited to the mixture of vinyltrimethoxy silane and 2-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane based on silane; The mixture of MTMS and 2-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane; Glycidoxypropyltrimewasxysilane, the mixture of 2-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane and MTMS; And the mixture of glycidoxypropyltrimewasxysilane and 2-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane.
Top invention of summarizing has overcome the difficulty that in use runs into brittle oxide substrate such as glass.Method of the present invention is being compared with the substrate intensity before the uncoated, and dramatic also unexpectedly increasing promptly recovered the intensity of brittle oxide substrate.Further be, coating of the present invention is transparent, and can be used in safely in the brittle oxide substrate, except increasing the intensity of promptly recovering substrate, coat preferably of the present invention does not influence mark, and this is a problem that applies in the substrate in the past always.
Should be understood that aforesaid summary and below to be described in detail all be exemplary, illustrative, can not limit the present invention defined in claims.
The brittle oxide substrate of using in the inventive method can be by the oxide material of any fragility, as aluminium oxide or aluminate, and silica or silicate, titanium oxide or titanate, germanate or constituted by the glass that above-mentioned substance is formed.Further be, the brittle oxide substrate can be made any form, for example a vial.
Have the following formula structure after the composition hydrolysis in the aqueous solution based on silane:
(OH)
3SiR " wherein R " is meeting or a organo-functional group that can hydrolysis in the aqueous solution.This organo-functional group can comprise the residue of hydrolyzable silane.R " selection also to make gained contain hydrolysis based on the aqueous solution of silane after applying and being solidificated in the brittle oxide substrate; can improve the intensity of brittle oxide substrate significantly, and can not influence the mark of brittle oxide substrate.
" preferred example comprises glycidoxypropyl, 2-(3,4-epoxy radicals cyclohexyl) ethyl, 3,3-dimethoxy propyl group, 3-urea groups propyl group and their hydrolysed form to R.
Therefore, the preferred example based on silane of hydrolysis comprises the glycidoxypropyltrimewasxysilane of hydrolysis, the 2-(3 of hydrolysis, 4-epoxy radicals cyclohexyl) 3 of the 3-urea groups propyl trimethoxy silicane of ethyl trimethoxy silane, hydrolysis and hydrolysis, 3-dimethoxy propyl trimethoxy silicane.
The applicator that puts on the brittle oxide substrate also can be the mixture based on silane of two or more hydrolysis.The mixture based on silane of two or more hydrolysis is particularly favourable, because people know, a kind of composition based on silane of hydrolysis can provide superior mark, and the composition based on silane of another kind of hydrolysis then can provide the superior performance that intensity is increased.Like this, a kind of mixture will provide required two kinds of character and balance, and the coat that promptly obtains can improve intensity does not influence mark again.For example, the mixture of the CETMO of hydrolysis and MTMS (MTMO) just can be used for obtaining this balance of performance.
Can be used on two or more hydrolysis based on the hydrolysis in the mixture of silane based on silane, other example also has: the methacryloxypropyl trimethoxy silane of hydrolysis, the 3-urea groups propyl trimethoxy silicane of hydrolysis, 1 of hydrolysis, two (trimethoxysilyl) ethane of 2-, 1 of hydrolysis, two (the 3-trimethoxysilyl propoxyl group) ethane of 2-, 5 of hydrolysis, 6-epoxy hexyl trimethoxy silane, the N-of hydrolysis (trimethoxy monosilane propyl group) maleic amide, the dimethyl tetramethoxy disiloxane of hydrolysis, and the N-of hydrolysis (3-triethoxysilylpropyltetrasulfide)-4-maloyl group amine (HBTEO), these compositions, for example, can be mixed together use with the CETMO of hydrolysis and/or the GPTMO of hydrolysis and/or the DPTMO of hydrolysis.In general, the multiple composition based on silane that is used in the mixture can add in the ratio that equates.Certainly, if need stronger mark, should add volume more, the CETMO of hydrolysis for example, the GPTMO of hydrolysis or the DPT-MO of hydrolysis further are any composition described here, if do not consider mark, can make separately to be used for improving significantly the intensity of brittle oxide substrate.
State that unless add what use all is by Union Carbide based on silane in specific embodiment, Doio corning, Huls America and PCR, Inc sells.
Though coating of the present invention can be the mixture based on silane of two or more hydrolysis, also can being applied to successively on the surface of brittle oxide substrate as coating with different hydrolysis based on silane.For example, apply the CETMO coat earlier for the surface of brittle oxide substrate, be still under the wet situation that is or does at the CETMO coat then, or after solidifying, apply different (as the MPTMO) coat of another layer CETMO coat or material.
Coat is the coat of the after-applied any number of plies of elder generation according to said method.Further be, can also apply surfactant with the method, promptly with hydrolysis based on silane to the brittle oxide surface-coated before and/or afterwards, apply with surfactant.After applying coat of the present invention, even also can also apply the coat that looks like (United States Patent (USP) 4,891, No. 241) such as Hashimoto.
Should be noted that the present invention applies coat for the brittle oxide substrate, also comprise to any applying coat of the present invention again on the material of precoating in the brittle oxide substrate.The example of coat is included in the hot junction coat of using usually in the industry in advance.
What be used for the inventive method can account for the 1-99% (weight) of the water or the aqueous solution based on the mean concentration of silane in the aqueous solution, is preferably 1-30% (weight), is more preferably 2-10% (weight).
For the aqueous solution based on silane that contains hydrolysis, for preparing the aqueous solution of the present invention, the water that is added in the composition based on silane is that the concentration according to the required aqueous solution decides.A kind of rarer hydrolysis based on silane, this vocabulary shows: the intensity of brittle oxide substrate has obvious improvement, the aqueous solution that contains based on the composition of silane that needs to apply is rarer.
Here used " solution " speech comprises: chemical solution, suspension, emulsion and mixture, any in them all have the complete or incomplete situation of internal mix.
The aqueous solution based on silane that contains hydrolysis can once prepare, and this is meant in manufacturing firm and just will be added to the water based on the composition of silane.Another kind method is, the composition based on silane of hydrolysis is made pure substance or concentrate earlier, by the user its water diluted then, makes the aqueous solution based on the composition of silane that in fact is used to be coated in the suprabasil hydrolysis of brittle oxide.
Further be, the present invention contain hydrolysis based on there not being the machine solvent in the aqueous solution of silane basically, this shows in the solution that do not have a mind and adds organic solvent.But, some organic compound as impurity and/or based on the composition of silane when solidifying and the accessory substance of water or reactant aqueous solution can exist.In addition, some commercially available compounds based on silane may contain organic solvent, and it is diluted in introducing the aqueous solution time, and the percentage of result's these organic solvents in the aqueous solution approximately is equal to or is less than the concentration of silane.An one example is UPTMO.
Certainly, people know, add the stability that solvent can increase solution.
Following reaction equation has been listed two-step reaction, it is believed that it is the two-step reaction that takes place in preparation with when using based on the aqueous solution of the composition of silane that contains hydrolysis.
In this reaction equation, trialkoxy silane reaction earlier in water forms three silanols in the solution.Three silanols in solution can contain oligomer.Then, during curing, three silanols in solution form siloxanes (Si-O-Si) coat of polymerization crosslinking with regard to condensation.This siloxanes (Si-O-Si) coat generally contains a kind of organic substituent, as R " group.
In this reaction equation, R ' O can be hydrolyzable any group.Following R ' group can satisfy this standard :-CH
3,-C
2H
5With
But the technical staff in this field knows some other group that also has that satisfies this standard.
The R group is that " organo-functional group of group, this organo-functional group can be residues of hydrolyzable silane to a kind of formation R that can hydrolysis.Behind hydrolysis, if the R group is hydrolyzable, " group contains at least one hydroxyl (OH) to R.If the R group is a non-hydrolysable, when being vinyl or methyl as R, then R and R " are identical.In general, the R group in above-mentioned reaction equation is advantageously selected to and makes the composition based on silane of the present invention can or recover in improvement to provide suitable balance aspect intensity and the mark two.Therefore, the preferred example of R has glycidoxypropyl, 2-(3,4-epoxy radicals cyclohexyl) ethyl, 3,3-dimethoxy propyl group and, so, " the better example of group just will be the hydrolysate of above-mentioned these better R compounds to R.
Above-mentioned reaction equation means the method based on the aqueous solution of silane that preparation contains hydrolysis that limited absolutely not.Can be at an easy rate with any hydrolyzable silane, for example the halogenated silanes class replaces trialkoxy silane as the trichlorosilane that replaces.
As mentioned above, the R group just becomes the R " group that contains the OH hydroxyl after hydrolysis.For example, the CETMO and the GPTMO of epoxide ring arranged in its R group, during hydrolysis, opened the ring of epoxy material in the aqueous solution, obtain a dihydroxy, " remainder of group then is still hydrophobic R.Like this, " balance of hydrophilic nmature (being provided by the OH group) and hydrophobic property just has been provided group R." hydrophily in the group all has special improvement effect to intensity and mark to R.
Can in the aqueous solution that contains hydrolysis, add surfactant based on the composition of silane, make the aqueous solution that contains hydrolysis cover the brittle oxide substrate surface better based on the composition of silane, the better effects if that brittle oxide substrate is as a result strengthened, outward appearance is also better.In general, only need to add a spot of surfactant, will make the silane-coating thing cover better in the suprabasil distribution of brittle oxide.At this on the one hand, non-ionic surface active agent is particularly effective.An example of this class surfactant is commercially available Triton X-102 (production of UnionCarbide company), and it is an octylphenoxy polyethoxy ethanol.Generally can add about 0.001-1.0% (pressing total restatement of solution) surfactant, be preferably adding about 0.001-0.05% (pressing total restatement of solution) surfactant.
The person skilled in art knows, in order to improve wetability, or in order to provide such as effect purposes such as the ultraviolet stability or the control rheological equationms of state, can add other compound in the aqueous solution that contains based on the composition of silane.
Contain pH based on the aqueous solution of silane, generally be adjusted in the scope of 1.5-1.2, scope is about 2-4 preferably, because test shows, the aqueous solution is the most stable in this pH scope, in general, " group is regulated the pH based on the aqueous solution of the composition of silane that contains hydrolysis according to selected R.Add alkalescence or acid compound, the pH of the aqueous solution can be transferred to required value.
Contain hydrolysis the aqueous solution based on silane, its performance can be because of aging and influenced, and finally its degree of improving brittle oxide substrate intensity can decrease.What is interesting is, in some cases as GPTMO, slight aging be useful; But further wear out performance is reduced.The shelf life based on the aqueous solution of silane that contains hydrolysis determines the wherein composition of composition, for example, is the aqueous solution of the CETMO of hydrolysis for its hydrolysis based on silane, its shelf life may at least 100 days, and its ability of improving brittle oxide substrate intensity is not subjected to obviously to influence in this time limit.
This aqueous solution that contains hydrolysis based on silane, be drip with spraying, drenching, dipping, brushing or anyly be suitable for applying liquid, steam or aerocolloidal other method deposition or be coated on the substrate surface.Ideal method is with conventional spray appliance, to apply the aqueous solution based on silane that contains hydrolysis in the sprinkling step of (for vial) commodity production of existing glass container and processing.
Applicator of the present invention can directly be applied to (for example, inner surface, the inside and outside surface of outer surface or part) on any surface of brittle oxide substrate, also can be applied to it and form on the skin different with brittle oxide substrate composition.For example, applicator of the present invention can be applied to tin-, titanium-, silicon-other metal-oxide layer on or on the mixture layer of this class material, and still effective for strengthening its brittle oxide substrate.
In producing such as the glass container of vial, typical way is that glass container passes through 1 at production line) a hot junction ventilator cowling, container is applied one deck inorganic tin compound, as tin oxide; 2) annealing furnace; And 3) lubricant sprays step.When using method of the present invention, then preferably after coming out, glass container contains coating based on the aqueous solution of silane from annealing furnace, and this step is considered to cold junction and applies.
Apply and contain based on the aqueous solution of silane and can carry out being lower than under any temperature of this aqueous solution boiling point, but generally in room temperature or near room temperature.
And, applying though contain can be higher than in the surface temperature of brittle oxide substrate (for bottle) under any temperature of aqueous solution freezing point based on the aqueous solution of silane, the surface temperature of brittle oxide is preferably 20～200 ℃, preferably 50～60 ℃.
In case brittle oxide substrate (as vial) with contain based on the aqueous solution of silane coated with after, just enter a solidification equipment, as solidifying case, wherein the surface of brittle oxide substrate generally reaches at least about 330 ℃.Surface temperature is lower than 230 ℃ when using as some of BTMOE based on the applicator of silane, also may solidify effectively.In case reach this temperature, just solidify.For example, surface temperature can keep 30 seconds down at least 230 ℃.The temperature of using when solidifying must be enough high, makes to apply to know that the suprabasil coat of brittle oxide solidifies, but unlikely overstrike.Effectively the temperature range of solidifying partly depends on selected R " group.For example, for the CETMO of hydrolysis, general temperature just is lower than 200 ℃, can obtain MIN solidification effect, and temperature is higher than 350 ℃ and can makes the applicator charing.
Curing schedule in the inventive method can be undertaken by the energy that applies any source, this energy should be enough to remove as water or other non-coating product from the surface of processed brittle oxide substrate, can not destroy brittle oxide substrate or coating material as long as apply this class energy.Curing schedule as energy and time pooled function can comprise the time that low-yield use is long, or opposite is, uses its suffered restriction of high-energy, as above-mentioned holding the relatively shorter time.The example of this class energy source comprises microwave, infrared, ultraviolet (uv), irradiation, place room temperature or higher temperature (as in electronics or coal gas heating cabinet) or certain combination of above-mentioned energy source condition.Pressure can be higher or lower than atmospheric pressure.
After finishing curing schedule, can use the lubricant of above-mentioned routine spray step to the brittle oxide substrate apply one deck such as poly polymerization coat to reach lubricated purpose.Having adopted coat lubricant of the present invention is the same good to its adhesion and lubricant to the adhesion of above-mentioned hot junction coat thing at least.
Use applicator of the present invention, might in the brittle oxide substrate, obtain sufficient lubricity, so just can with lubricator not spray step, especially be suitable for the manufacturing of a vial.
Intensity described here is meant goods (and damage) the portative peak load of sample before of breaking, and has many distinct methods to can be used to measure breakdown strength, looks the purposes of the geometry of sample and goods and different.They comprise bending strength, vertical load strength, burst strength, concentric ring intensity and impact test intensity.
Method of the present invention can strengthen the brittle oxide substrate really.As described in the background technology part, in theory, all brittle oxide substrate, particularly glass can damage because of the existence of small defective or small amount of impurities is final.Since the brittle oxide substrate should have much higher intensity in theory, method of the present invention the present invention can be characterized by a kind of method of recovering brittle oxide substrate intensity, because can make its actual strength comparatively approach its theoretical strength for the brittle oxide substrate provides intensity to a certain degree.
Adopt Journal of Strain Analysis vol19, No.3 (1984) and Journalof Non-Crystalline Solids 38 ﹠amp; 39, the test that this this those skilled in the art of the described concentric ring strength test of pp419-424 (1980) understand, be measure with or a kind of method of the brittle oxide substrate actual strength that applies with the aqueous solution that contains hydrolysis based on silane.The method of another measured intensity is to carry out the burst pressure strength test with ASTM test C-147 described employing slope pressure testing machine (by AGR, Intl.Literature obtains), and this also is the general methods of also understanding of these those skilled in the art.
Another method of measured intensity is to adopt impact strength test, and this method has been narrated in the specification of AGR shock machine.This test is approved that by industrial it is to adopt AGR, Int ' l.Butler, the AGR impact test apparatus that PA produces.This strength test also is that the person skilled in art understands.
Before point out, use the aqueous solution that contains hydrolysis of the present invention based on silane, can improve the intensity of brittle oxide substrate significantly.Concentric ring intensity, burst pressure intensity or impact strength test show that this significant improved strength has 10% at least, preferably under the situation, and improved strength at least 20%.
The person skilled in art will appreciate that the intensity of brittle oxide (as glass) substrate or goods if increase is arranged, and then adopts and makes the goods that are equal to and have the common mechanical performance substantially on the intensity, and the quantity of needed oxide base is just lacked.Like this, in the glass container specific embodiment as bottle, bottle will be than undressed same bottle more lightly.In addition, increased intensity, can make product damaged chance be arranged in actual use still less.
Indicate in theory, the silane that polymerization crosslinking all can take place between coat inside and coat and brittle oxide substrate surface connects.Be attached to lip-deep coat owing on defective surface, form the Si-O-Si network, the effect that fine fisssure is gone up on the surface of repairing is just arranged.Form siloxane bond at defect area, just increased the glass strain of goods.
In fact repair or increase its intensity for the sample of damaged once with coat, will make the lip-deep stress concentration effect that bears tension force be reduced to Min..This just requires the defective in the surface of bearing tension force is carried out partially or completely reparation.The bottle wall is bandy when increasing for the glass pressure of withstanding pressure test.In general, when bearing load, be that meeting produces protruding in distortion on the outer surface.
But, also can increase the impact failure load of sample and needn't recover the intensity of substrate.Its method is to utilize the lip-deep coat that is impacted, rather than utilizes that surface of bearing tensile stress.(impact load generally is to produce tensile stress on the inner surface of container).Enhancing mechanism in this case is that coat can absorb the energy that impacts, and energy can't be delivered to the destruction amount of impact load of measuring in the substrate with the form of bending stress as a result will increase, but the bending strength of object does not then change.
The glass container of commodity production generally applies the layer of metal oxidation film with chemical vapour sedimentation method immediately after making; This is called hot junction coat (HEC).In general, this coat is a tin oxide, but also can be titanium oxide or other metal oxide, and also can contain other component and improve some physical propertys, as electric conductivity.Generally about 50-125 is thick for this coat.The HEC of deposition exists no matter have or not in advance on the surface, and the present invention can both recover or increase impaired glass intensity.
About the mark of brittle oxide substrate, should be understood that as described above the hydrolysis of some curing of the present invention can't influence mark based on the coat of silane.Mark is to test with following label peeling to measure.
Use has 4 angles, and area is about 6 inch
2Label paper, before, this label paper is weighed it being applied casein type adhesive (National Starch sell 4242).0.6 gram casein type adhesive is added in the back side (reverse side) of label, and then rolls in the above with 5mm glass bar or similar object adhesive is coated on the label equably.Label is pressed on the surface of brittle oxide substrate at room temperature dry minimum 2 hours.From each angle of label hand strip off label, all some is torn from substrate on each angle of label.If still stay on the surface of brittle oxide substrate greater than the label of 50% (weight), then can think suprabasil coat for target of the present invention, its mark is an acceptable.
Be preferably, the mark of the brittle oxide substrate through applying calculates according to the % that stays the label on the brittle oxide substrate surface (weight), be greater than about 60%, more preferably greater than about 70%.
The intensity that coat produced of solidifying in the brittle oxide substrate is significantly improved, and is that prolonged tolerance is arranged for the deleterious effects of humidity.In fact, anti-moisture test is to determine coat of the present invention can make on the brittle oxide substrate surface through improving a degree acceptable method how of the intensity maintenance that promptly recovers.The lasting moisture-proof that is shown by the coat that the present invention is based on silane is that well it generally depends on R " group again.Measure the humidity effect of moisture to coat of the present invention, method is its coat to be solidified the back kept being less than 3 hours coating brittle oxide substrate under the condition of relative humidity general about 40% intensity compare with the intensity of the identical coating brittle oxide substrate that has stood 30 days 90% humidity.In this test, the moisture-proof that puts on the suprabasil cured coated layer of the present invention of brittle oxide shows as the change 50% of intensity, and is better only about 20～30% under the situation, and best about 0～10%.Such moisture-proof is good, and this is more suitable as the vial that uses in U.S. south in the high humidity environment.
What is interesting is that the coat based on silane of not every hydrolysis all has good moisture-proof after being coated in the brittle oxide substrate.For example, as a comparison, as R " be the composition based on silane of the hydrolysis of vinyl or methyl be applied to solidify in the brittle oxide substrate after; the intensity of substrate has had obvious the improvement [as " 110% raising (concentric ring test) being arranged when being vinyl as R, as R " 200% raising (concentric ring test) is arranged when being methyl]; and its moisture-proof is also very excellent; as [R " is 0% loss of strength (keeping 100% intensity) when being vinyl, as R " when being methyl; be 0% loss of strength (promptly keeping 100% intensity)]; still; if " be 2-(3 with R, 4 epoxy radicals cyclohexyl) hydrolysis of ethyl or glycidoxypropyl based on silane be coated in the brittle oxide substrate solidify after, though after applying the intensity of substrate also have clear improvement (as, as R " when being 2-(3; 4 ring ethyoxyl cyclohexyl) ethyl; have 200% to improve; be the center ring test); as R " when being glycidoxypropyl, 200% raising is arranged), but moisture-proof only belongs to still good level, as R " when being 2-(3; 4 epoxy radicals cyclohexyl) ethyl; loss of strength 40～50%; intensity keeps 50～60%, as R " when being glycidoxypropyl, loss of strength 90～100% (intensity keeps 0～10%)].
If compare the mark of these coats, then more interesting:
R "
Mark
Methyl 0%
Vinyl 0～10%
2 (3,4 epoxy radicals cyclohexyl) ethyl＞60%
Glycidoxypropyl＞60%
But, as previously mentioned, be applied to the applicator of brittle oxide substrate, also can be the mixture based on the composition of silane of two or more hydrolysis.
For example, the present invention has had been found that the mixture that obvious improvement intensity and excellence mark and moisture-proof can be provided." be the mixture based on the composition of the hydrolysis of silane of methyl and 2-(3,4 epoxy radicals cyclohexyl) ethyl, be exactly a good example to R.More interest is, after this class mixture was made, the neither one component can have adverse influence to any required character in the mixture.For example, the existence of MTMO can not influence mark.
The aqueous solution based on silane that contains hydrolysis of the present invention does not have combustibility, and this is not particularly because there is the cause of organic solvent basically in the aqueous solution.
When the oxide base that applies fragility particularly during glass container, the composition based on silane of hydrolysis is preferably invisible on container.When solidifying, silane coating also should nondiscolouring, also should not demonstrate texture structure.The composition based on silane of hydrolysis of the present invention just meets this standard.It should be noted that in some commercial use, need coating (seemingly being dense fog or fresco shape) of disperse only.Can apply temperature (for example being the surface temperature of brittle oxide substrate) and be maintained at about 80～100 ℃, coat of the present invention also will have this outward appearance of filling the air.
Moreover, can also in the aqueous solution, add as coloring agent, make coat have color.The example of suitable dye comprises the Celestine orchid, and Bismark is brown and Erochrome black.
In addition, also can in the aqueous solution, use dyestuff, be used to refer to the degree of solidifying and spraying covering.In addition, the aqueous solution can also comprise other component, as UV retarding agent and fluorescer.Containing fluorescer can make the substrate that is coated with brittle oxide have the character of " luminous in the dark ".
Applicator of the present invention also has a benefit, is exactly that it can hide the visible vestige that frays on the substrate surface.This point particularly needs in the industry of using the bottle that can recharge dress, because owing to circulate through many times using, generally produced the vestige that turns white at the bottle periphery on the filling production line.
The present invention will illustrate further that by some following embodiment these embodiment only are examples of the present invention.Embodiment 1
In this embodiment, on the soda-lime glass rod, impress the slight crack that produces size about 50 microns (μ m) in its surface with a Vickers (Vickers) diamond.These glass rod samples are carried out bend test until destruction, and recording its mean intensity is 56 MPas.To have of the aqueous solution spraying of the sample of same slight crack defective with 10% (weight %) vinyltrimethoxy silane (VTMO).This solution contains enough sulfuric acid is adjusted between 3.0 and 3.4 pH.After this, 200 ℃ with this sample heat treatment 15 minutes, make bend test then.The mean intensity of sample is increased to 90 MPas from 56 MPas like this.Embodiment 2
Embodiment 2 is modification of embodiment 1.In the present embodiment, sample also is a rod of carving trace, and solution is 10% (weight) VTMO, and is acidified as described in the example 1.This solution also contains the non-ionic surface activator (Triton X-102) of 0.75% (weight).After solidifying, this has the intensity of trace sample to be increased to 93 MPas from 56 MPas.Embodiment 3
Embodiment 3 is identical with embodiment 1, except used silane is MTMS (MTMO).The mean intensity of control sample is 62 MPas.After applying and solidifying, bending strength increases to 96 MPas.Embodiment 4
Embodiment 4 is repetitions of embodiment 2, uses MTMO, and average control intensity remains 62 MPas, but the sample average that strengthens is 103 MPas.Embodiment 5 and embodiment 6
Embodiment 5 and embodiment 6 are respectively the repetitions of embodiment 1 and 2, and different is that used silane is isobutene acyl-oxygen (base) propyl trimethoxy silicane (MPTMO).These samples, average control intensity are 60 MPas.
After applying, these samples are heating and curing as described above, but also additional simultaneously UV irradiation is to strengthen solidification.The mean intensity that embodiment 5 strengthens sample reaches 126 MPas, and the enhancing sample of embodiment 6, mean intensity reaches 124 MPas.Embodiment 7
This embodiment has illustrated the disposition that has produced the plate glass sample that can control slight crack with the vickers diamond impression.Slight crack on this sample is of a size of 90 μ m.These samples apply with the solution that contains three kinds of identical weight ratio silane.Total silane concentration is 10% in the water (weight), and the amount of every kind of silane is about 3.33% (weight).Solution contains the sulfuric acid of capacity, makes pH between 3.0～3.4.The non-ionic surface active agent that adds 0.75% (weight) is to increase wetability.In this 1: 1: 1 solution glycidoxypropyltrimewasxysilane (GPTMO), 2-(3,4 epoxy radicals cyclohexyl) ethyl trimethoxy silane (CETMO) and MTMO.
The intensity of contrast is 45MPa, and solidifies the sample of (125 ℃ of curing in 15 minutes are followed, 225 ℃ of curing in 10 minutes) with 1: 1: 1 solution coating processing through two steps, and its intensity is 160MPa, has increased about 3.5 times.Even MTMO (when it used separately, the mark that provides was bad) is present in this design of mixture, this mixture has still provided good mark.Embodiment 8
With containing 1:1GPTMO and CETMO, its total concentration also is the solution of 10% (weight), identical device product has in the same old way been carried out the enhancing coating processing to embodiment 3 is described.This solution also contains makes the capacity sulfuric acid of pH between 3.0 and 3.4.These samples have also passed through embodiment 3 described heat treatments.Do not use the sample of coat, intensity is 45 MPas, increases to 118 MPas after having used this coat, and intensity has increased about 1.6 times.Embodiment 9
On the sidewall of amber glass bottle, also produced identical slight crack earlier as the method among the embodiment 3.These have the average burst pressure of slight crack defect container is 1.9MPa.Use the CETMO solution and the embodiment 3 described identical curing schedules of 10% (weight) then, the bottle that the slight crack defective is arranged has been carried out silane treatment.Average burst strength through the sample of this processing increases to 3.2MPa, has increased by 68% than defective control sample.Embodiment 10
Produced slight crack as embodiment 3 and 9 described 12 ounces of (OZ.) beer bottle impressions to some standards.The burst pressure of these defectiveness containers is 1.9MPa.As described in embodiment 7,1: 1: 1 solution has carried out applying and solidifying average burst strength increases to processed sample from the 1.9MPa of control value 3.5MPa to sample.Embodiment 11
By above-mentioned method, 12 ounces of bottles impressions of lightweight have been produced slight crack, apply with embodiment 9 described 10%CETMO solution.The average burst pressure of the control bottle through impressing is 1.5MPa.And, solidifying the bottle of (as described in embodiment 3) then through spraying coating, its average burst pressure increases to 2.6MPa.Embodiment 12
CETMO solution with 10% weight applies 12 ounces of bottles of lightweight of receiving state, and the burst strength of control sample is 1.6MPa, and through being coated with the sample of curing, average burst strength is 3.0MPa.Embodiment 13～16
In these embodiments, on sodium calcium plate glass sample surfaces, impress formation as embodiment 1 described 50 μ m slight cracks with vickers diamond.These samples are tested with a kind of center ring anchor clamps.The mean intensity of the sample of these uncoated is 69MPa.Embodiment 13
Prepare the suspension of MPTMO.Its method for making is earlier to suitable acid such as H
2SO
4Be acidified to pH and be in 2.5 the water and add silane, obtain the mixture of 10% (weight).Add 0.5% (weight) Triton X-102 again, then room temperature aging 24 hours of the composition solution of ordering.At room temperature, the oligomer of polycondensation has been separated after 24 hours, forms suspension.This suspension is drenched a zone that the slight crack defective is arranged that is applied to plate glass, then 125 ℃ of following heat treatments 15 minutes,, handle through ultraviolet curing again.The mean intensity of the plate glass of Chu Liing is 223MPa like this.Embodiment 14
The 10 described identical steps with embodiment are arranged, prepared the suspension of 10% (weight) methacryloxypropyl methyldiethoxysilane (MPMDEO), but used the surfactant of 1% (weight) content.This suspension drenched to drip to apply be coated on the plate glass, solidified 15 minutes down at 125 ℃, and then solidified 10 minutes down at 225 ℃.Through the plate glass sample of this processing, its mean intensity is 143MPa.Embodiment 15
It is described to press embodiment 10, has prepared the suspension of 10% contain 1: 1 (weight) dimethyl tetramethoxy disiloxane and MPMDEO, and different is with acetate pH to be transferred to 3.5, and does not add surfactant.Sample has carried out two-stage cure as described in the embodiment 14.Mean intensity through the plate glass sample of this processing is 193MPa.Embodiment 16
Except using H
2SO
4PH is adjusted to 3.5, and adds outside 0.025% (weight) TritonX-102, other is as the suspension of the mixture that makes 10% (weight) (weight) two-uncle-butoxy diacetoxy silane (DBDAS) that contains 1: 1 and MPMDEO as described in the embodiment 14.Sample is by the embodiment 12 described two-stage cures that carried out.Through the plate glass sample of this processing, its mean intensity is 152MPa.Embodiment 17
In this embodiment, with vickers diamond impression sodium calcium plate glass, produce the slight crack defective of about 50-μ m.Sample is tested with center ring anchor clamps, and mean intensity is 69MPa.With acetate the solution of 10% (weight) DBDAS in water is regulated pH to 3.5.This solution dropping is coated on the flat samples, 125 ℃ of following heat cures 15 minutes.Mean intensity through solidified sample is 133MPa.
Embodiment 18
As embodiment 17, handle the plate glass sample.Use H
2SO
4The aqueous solution of 10% (weight) GPTMO is regulated pH to 3.5.After this solution at room temperature placed for two weeks, drip with solution and to be coated on the crackled glass sample, solidify 15 these clocks down at 125 ℃ earlier, solidified 10 minutes down at 225 ℃ then.Mean intensity is 219MPa.Embodiment 19
On sodium calcium plate glass sample, stamp out an impact defective of easily seeing with the golden guiding principle stone of circle point.The average concentric ring intensity of this sample is 43MPa.
PH H with the aqueous solution of 30% (weight) CETMO
2SO
4Transfer to 3.5.This solution dropping is coated on the glass sample of above-mentioned defective, 125 ℃ of heat cures 15 minutes, and then 225 ℃ of heat cures 10 minutes.Mean intensity is 61MPa.Embodiment 20
On some sodium calcium plate glass, impress the slight crack that produces about 50 μ m with dimension formula diamond.These samples are tested with the concentric ring anchor clamps.Mean intensity is 69MPa.
With undiluted MPTMO the plate glass sample has been carried out drip applying, then by energy level at every turn by be 5.3 Jiao Er/centimetre
3The UV curing apparatus, common mistake three times.The sample of Chu Liing like this, its mean intensity is increased to 104MPa.Embodiment 22
Press the method for embodiment 21, carry out coining manipulation, then coated with the SnO of pyrolysis at sodium calcium plate glass sample
2Thick to 150 .Sample is annealed then, removes residual stress.The control sample that this tin oxide applies, intensity is 83MPa.
To SnO
2The sample that applies is used embodiment 3 and 4 described 10% (weight) MTMO solution-treated then, and producing intensity is the sample of 210MPa.Embodiment 23
On sodium calcium plate glass sample, impress the slight crack that produces about 50 μ m with vickers diamond.Tested these samples with the concentric ring anchor clamps, mean intensity is 69MPa.Preparation 10% (weight) 3, the aqueous solution of 3-dimethoxy propyl trimethoxy silicane (DMPTMO) transfers to 3.5 with pH.After at room temperature leaving standstill 2 hours, a part of solution drips and is coated on the glass sample of crackle, solidifies 15 minutes down at 125 ℃ then, solidifies 10 minutes at 225 ℃ again.Through the glass sample of this processing, mean intensity is 88MPa.DMPTMO solution is analyzed through 1H nuclear magnetic resonance (NMR), only demonstrate silantriol-CH (OCH
3)
2Group is at 4.41 (triplet) ppm.
After this solution of another part at room temperature leaves standstill 192 hours, be used for dripping and be coated on other glass samples that same crackle is arranged, just be cured as mentioned above then.The mean intensity of these glass samples is 256MPa, and this solution is analyzed through NMR, and respectively in 4.55 (three-way), 4.90 (triplet and 9.63 (single line) ppm shows silantriol-CH (OH) CN
3) ,-CH (OH)
2With the existence of-CHO group, the ratio that they are the abundance of balance is about 4: 4: 2.Embodiment 24
The present invention is tested according to following process in a system bottle factory: before with AGR slope pressure testing machine test, carry out pressure test for earlier 120 soft material bottles of 16 ounces of glass.Average burst pressure is 422psi (2.9MPa), and the bottles break percentage that is lower than 300psi (2.1MPa) is 15%.The process of used processing uses solution of the present invention (specifically being CETMO) to spray exactly, and 230 ℃ or more carry out heat cure under the high humidity, the cold junction that carries out standard then applies.Treated 120 containers have carried out burst pressure tests with method as hereinbefore, obtain average burst pressure 490psi (3.4MPa), improved 16% than situation about handling without the present invention, the percentage of damage that is lower than 300psi (2.1MPa) is that 6% ratio has descended 57% without the situation that the present invention handles.Embodiment 25
Through the float glass of vickers diamond impression, be 3.5 with pH, 10%3-urea groups propyl trimethoxy silicane (UPT-MO) aqueous solution that contains 0.05%Tri-ton X-102 surfactant drips and applies.Sample was handled 10 minutes at 225 ℃ more subsequently earlier 125 ℃ of heat treatments 15 minutes.Concentric ring intensity is:
Uncoated 9588psi (66.1MPa)
Through applying 25492psi (176MPa) embodiment 26
Except silane is with 1, outside two (trimethoxysilyl) ethane of 2-, other all repeats embodiment 25.The average concentric ring intensity of control sample is 11566psi (79.8MPa).After coating and the curing, average concentric ring intensity is 19728psi (136MPa) embodiment 27
Except the heat treatment product are that other all repeated embodiment 26 125 ℃ of heating 15 minutes.The mean intensity of no coat is 11566psi (79.8MPa), and rises to 23799psi (164MPa) after coating and the curing.Embodiment 28
Except silane is 1, outside two (the 3-trimethoxysilyl propoxyl group) ethane of 2-, repeat embodiment 25.Prepare BTMOPE with following process.
In 1.5 hours, 0.7 mole of allyl bromide, bromoallylene is added drop-wise in the mixture of 0.33 mole of ethylene glycol of stirring, 1.25 mole of 50% sodium hydrate aqueous solution and 0.025 mole of tributyl-methyl phosphonium ammonium chloride.Mixture was heated 12 hours at 80～90 ℃.Make mixture be cooled to 25 ℃, separate and aqueous phase discarded.Organic facies then with the ether dilution of 5 times of volumes, is washed with saturated sodium chloride solution, then through dried over sodium sulfate.Decompression distillation isolates 1 under boiling point 89-90 ℃ of (50 holder) condition, and two (allyloxy) ethane of 2-are BAOE.
(Huls America, Cat#PC072) heating is 85 ℃ for the mixture of mixture in dimethylbenzene in dimethylbenzene with 0.075 mole of BAOE and 50 microlitre divinyl platinum complexs.In this mixture under inert atmosphere 0.160 mole of trimethoxy silane of agitation and dropping, for the time two hours.Mixture was stirred 2 hours decompression distillation then down at 85 ℃.BT-MOPE draws as the cut separation that at 0.25 holder boiling point is 135～136 ℃.After coating and the curing, the concentric ring intensity of sample rises to 29183psi (201MPa) from 10139psi (69.9MPa) (uncoated).Embodiment 29
Silane with embodiment 28 repeats embodiment 27.The sample strength that applies and solidify on average is 30153psi (208.0MPa), and the mean intensity of contrast is 10139psi (69.9MPa).Embodiment 30
In the 5%CETMO solution that also contains 0.025%Triton X-102 surfactant, add the blue dyestuff (CAS# 1562-90-9) of 0.5% (weight) Celestice.Then with 2.0 the gram solution (every bottle) with this spray solution on 16 ounces beverage bottle.These sample bottles are heat treated 33 seconds in 700 ℃ infrared heating heating furnace then.The bottle of this coating has uniform blue look coat.Embodiment 31
In the 10%CETMO solution that contains 0.05%Triton X-102 surfactant, add 1% (weight) Uvinul MS-40 (BASF AG's production) and 0.1% (weight) Tinopal CBS-X (production of Ciba-Geigy company).This spray solution on plate glass, is used the method heat treatment of embodiment 25 again.0.9 micron of last coating bed thickness.Measure its ultraviolet light transmittance respectively in the front and back that apply and solidify, the result is as follows:
Light transmittance %
Sample goes into=and 340nm goes into=380nm
Uncoated 89 90
Apply the back and solidify 5 27 embodiment 32
Prepared silane mixture as follows:
At room temperature 1 gram Nafion, 50 perfluoro acid resins, 2 gram (0.0085 mole) GPTMO and 2 gram (0.11 mole) deionized waters are added in the plastic bottle together.After 15 minutes, add 91.9 gram water, 3 gram (0.017 mole) MTEO (MTES) and 0.1 gram Triton X-120 again, obtain 100 gram solution altogether.
This solution (at 20 days in addition in 1 hour) is sprayed onto with an AGR line simulator on 16 ounces of beverage bottles that one minute pipe die intends, bottle surface temperature be 55 ℃, keep the bottle average surface temperature and under 225 ℃ of conditions, solidified 30 seconds.The burst strength of these bottles increases by 51% and 71% than untreated control thing respectively.
Use the 0.6 gram label (four angles are arranged) that contains 0.6 gram adhesive to bottle surface then.Make adhesive keep 16 hours (spending the night) in room temperature.Carry out removing label test (promptly with hand strip off label from each angle, until tearing its part off), had 75～80% labels keeping on this bottle.The solution left standstills that will contain 5 gram MTEO and 0.1 gram Triton X-102 with identical method spray after 1 hour and are applied on the identical bottle, also through wearing out, do not have residual (can not adhere to) through check tag.Embodiment 33
The alumina rod of square-section is carried out the what state that three point bending test strengthens it with check the inventive method.The alumina sample of half (6) is carried out check experiment by the three-point bending setting on the Instron Material Testing Machine.Second half sample applies with 10% (weight) CETMO/0.025% (weight) Triton X-102/0.025% (weight) RP-40 (German T.H.Goldschmidt produces) prescription, carry out two step heat treatments (1 25 ℃ 15 minutes, 225 ℃ 10 minutes) then and make its curing.The average burst strength of control sample is 23300psi, and treated sample, mean intensity is 28,200psi has on average increased by 21%.
In view of United States Patent (USP) 4,891,241 (Hashimoto etc.) have reported that when only using silane-coating, its intensity does not increase in its 25 hurdle 27～29 row comparative examples 1,2 and 3, and then the intensity improvement degree of embodiment of the invention processing gained is surprised in season mutually.As described herein, do not adopt such as the additional treatments in people's patents such as Hashimoto, but the glass of handling through the inventive method, the untreated contrast of its strength ratio is doubled and even more than one times, and the enhancing result who is observed, and difference is less.If consider that people's such as Hashimoto patent is on its 5th hurdle, places such as 36 row once pointed out only to be not enough to produce with the siloxane treated substrate intensity is improved, and a kind of polymer-coated layer is absolutely necessary for the development of the intensity aspect of its report, and then the improvement made of the present invention especially makes us surprised.
For a person skilled in the art, understand specification of the present invention and practical application thereof, just be not difficult to propose other embodiments.This specification and embodiment wherein should be considered to exemplary, and true scope of the present invention and spirit are then pointed by following claims.
Claims (48)
1. method that strengthens the brittle oxide substrate comprises step:
A) apply with containing based on the composition of silane and the aqueous solution that do not contain organic solvent substantially, wherein its in based on the composition of silane in the aqueous solution after the hydrolysis, its chemical formula is:
(OH)
3SiR " R " is an organo-functional group:
B) will form the layer of transparent layer on the applicator solidification brittleness oxide base,
Wherein, based on the R in the silane " selection the intensity of the brittle oxide substrate before (i) and the coating step is compared, have the substrate of the brittle oxide of cured coated layer, its intensity has tangible improvement; (ii) the coat of Gu Huaing can not influence the mark of brittle oxide substrate.
2. method according to claim 1, wherein R " be selected from glycidoxypropyl, 2-(3,4-epoxy radicals cyclohexyl) ethyl, 3,3-dimethoxy propyl group, 3-urea groups propyl group, their hydrolysed form with and composition thereof.
3. method according to claim 1, wherein said functional group is a residue of hydrolyzable silane.
4. method according to claim 1, wherein to record with label peeling test be greater than 50% to the suprabasil mark of brittle oxide.
5. method according to claim 1, it is greater than 60% that the suprabasil mark of brittle oxide wherein records with the label peeling test.
6. method according to claim 1, brittle oxide wherein is a glass.
7. method according to claim 1, wherein based on silane when solidifying and brittle oxide substrate generation chemical reaction.
8. method according to claim 1 wherein further contains at least a following material lubricant, dyestuff, fluorescer and/or UV retarding agent based on the combination spy of silane.
9. method according to claim 1 further comprises: apply the step of metal oxide for before the brittle oxide substrate in step (a).
10. method that strengthens the brittle oxide substrate comprises step:
A) apply with containing based on the composition of silane and the aqueous solution that do not contain organic solvent substantially, wherein its in based on the composition of silane in the aqueous solution after the hydrolysis, its chemical formula is:
(OH)
3SiR " R " is an organo-functional group:
B) will form the layer of transparent layer on the applicator solidification brittleness oxide base,
Wherein, based on the R in the silane " selection the intensity of the brittle oxide substrate before (i) and the coating step is compared, have the substrate of the brittle oxide of cured coated layer, its intensity has tangible improvement; (ii) by significantly improving of producing of the coat that solidifies in the brittle oxide substrate intensity, at least 50% prolonged moisture-proof is arranged.
11. method according to claim 10, wherein R " are vinyl or methyl.
12. method according to claim 10, brittle oxide wherein is a glass.
13. method according to claim 10, wherein based on silane when solidifying and brittle oxide substrate generation chemical reaction.
14. method according to claim 10 wherein further contains at least a following material lubricant, dyestuff, fluorescer and/or UV retarding agent based on the combination spy of silane.
15. method according to claim 1 further comprises: apply the step of metal oxide for before the brittle oxide substrate in step (a).
16. method according to claim 10, wherein said functional group is a residue of hydrolyzable silane.
17. a method that strengthens the brittle oxide substrate comprises step:
A) apply with containing based on the composition of silane and the aqueous solution that do not contain organic solvent substantially, wherein its in based on the composition of silane in the aqueous solution after the hydrolysis, its chemical formula is:
(OH)
3SiR " R " is an organo-functional group:
B) will form the layer of transparent layer on the applicator solidification brittleness oxide base,
Wherein, based on the R in the silane " selection the intensity of the brittle oxide substrate before (i) and the coating step is compared, have the substrate of the brittle oxide of cured coated layer, its intensity has tangible improvement; (ii) the coat of Gu Huaing can not influence the mark of glass container outer surface.
18. method according to claim 17, wherein said functional group is a residue of hydrolyzable silane.
19. method according to claim 17, wherein R " be selected from glycidoxypropyl, 2-(3,4-epoxy radicals cyclohexyl) ethyl, 3,3-dimethoxy propyl group, 3-urea groups propyl group, their hydrolysed form with and composition thereof.
20. method according to claim 17, wherein to record with label peeling test be greater than 50% to the suprabasil mark of brittle oxide.
21. method according to claim 17, it is greater than 60% that the suprabasil mark of brittle oxide wherein records with the label peeling test.
22. method according to claim 17, wherein the pH scope based on silane is 1.5～11.
23. method according to claim 17, wherein the concentration of composition in the aqueous solution based on silane is 1～99% scope.
24. method according to claim 17, wherein the composition based on silane is a kind of mixture of 2-(3,4 epoxy radicals cyclohexyl) ethyl trimethoxy silane, surfactant and acid water.
25. method according to claim 17, it is in 10～600psi scope that the intensity of wherein uncoated glass container records with burst pressure tests.
26. method according to claim 17, wherein the wall thickness of glass container is 0.1～6mm scope.
27. the brittle oxide container of a silane-coating comprises:
(a) brittle oxide container;
(b) be solidificated in polymerization crosslinking siloxanes hyaline layer on the brittle oxide vessel surface, the siloxanes of this polymerization crosslinking is that the aqueous solution based on the composition of silane by basic organic solvent-free forms, be selected from MPTMO, GPTMO, VTMO, CETMO, MTMO, DMPTMO, 3-urea groups propyl trimethoxy silicane, 1, two (trimethoxysilyl) ethane of 2-, 1, two (the 3-trimethoxysilyl propoxyl group) ethane of 2-, 5,6-epoxy radicals hexyl trimethoxy silane, N-(trimethoxy-silylpropyl) maleic amide, their hydrolysed form with and composition thereof.
28. container according to claim 27, wherein container is a vial.
29. container according to claim 27, wherein the wall thickness of vial is 0.1～6mm.
30. container according to claim 27, further being included on the transparent layer surface of polymerization crosslinking siloxanes has a label.
31. container according to claim 30, the suprabasil mark of brittle oxide wherein is by recording greater than 60% with the label disbonded test.
32. container according to claim 27 further comprises: between the hyaline layer of the outer surface of container and polymerization crosslinking siloxanes, the layer of metal oxide is arranged.
33. container according to claim 27 further comprises: on the polymerization crosslinking siloxane surface, be coated with one deck lubricant.
34. container according to claim 33, further being included in has a label on the lubricant application laminar surface,
35. method according to claim 1.Wherein said composition based on silane is the mixture of the CETMO of MTMO and hydrolysis, or the mixture of the GPTMO of the CETMO of MTMO, hydrolysis and hydrolysis, or the mixture of the GPTMO of the CETMO of hydrolysis and hydrolysis, or the mixture of the GPTMO of the CETMO of hydrolysis and hydrolysis, or the mixture of the CETMO of TMO and hydrolysis, or the mixture of the CETMO of the DEPTMO of hydrolysis and hydrolysis.
36. a method of recovering the brittle oxide substrate comprises step:
A) apply with containing based on the composition of silane and the aqueous solution that do not contain organic solvent substantially, wherein its in based on the composition of silane in the aqueous solution after the hydrolysis, its chemical formula is:
(OH)
3SiR " R " is an organo-functional group:
B) will form the layer of transparent layer on the applicator solidification brittleness oxide base,
Wherein, based on the R in the silane " selection the intensity of the brittle oxide substrate before (i) and the coating step is compared, have the substrate of the brittle oxide of cured coated layer, its intensity has tangible improvement; (ii) the coat of Gu Huaing can not influence the mark of brittle oxide substrate.
37. a method of bearing defective in the tensile surface of partially or completely repairing the brittle oxide substrate comprises step:
A) applied by the surface of tension force with containing to this based on the composition of silane and the aqueous solution that do not contain organic solvent substantially, wherein its in based on the composition of silane in the aqueous solution after the hydrolysis, its chemical formula is:
(OH)
3SiR " R " is an organo-functional group:
B) applicator is solidified, is subjected to the surface of tension force to form the layer of transparent layer,
Wherein, based on the R in the silane " selection the intensity that is subjected to tensile surface before (i) and the coating step is compared, have the tensile surface that is subjected to of cured coated layer, its intensity has tangible improvement; (ii) the coat of Gu Huaing can not influence the mark that is subjected to tensile surface.
38. according to the described method of claim 37, the wherein said tensile surface that is subjected to is the brittle oxide substrate.
39. according to the described method of claim 37, the wherein said tensile surface that is subjected to is a glass container.
40. a composition that is used for applying the brittle oxide substrate, it is a kind of mixture of CETMO and VTMO.
41. a composition that is used for applying the brittle oxide substrate, it is a kind of mixture of CETMO and MTMO.
42. a composition that is used for applying the brittle oxide substrate, it is GPTMO, a kind of mixture of CETMO and MTMO.
43. a composition that is used for applying the brittle oxide substrate, it is a kind of mixture of GPTMO and CETMO.
44. a composition that is used for applying the brittle oxide substrate, it is UPTMO.
45. a composition that is used for applying the brittle oxide substrate, it is 1, two (trimethoxysilyl) ethane of 2-.
46. a composition that is used for applying the brittle oxide substrate, it is 1, two (the 3-trimethoxysilyl propoxyl group) ethane of 2-.
47. a composition that is used for applying the brittle oxide substrate, it is a kind of mixture of DMPTMO and CETMO.
48. method according to claim 1, wherein the composition based on silane puts on the brittle oxide substrate under 80～100 ℃ of temperature, in order that produce a kind of outward appearance that light is filled the air after curing.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US7881193A | 1993-06-21 | 1993-06-21 | |
| US08/078,811 | 1993-06-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1113075A true CN1113075A (en) | 1995-12-06 |
Family
ID=22146358
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94190546A Pending CN1113075A (en) | 1993-06-21 | 1994-06-21 | Brittle oxide substrates strengthened by cross-linkable silanes |
Country Status (19)
| Country | Link |
|---|---|
| EP (1) | EP0655953A4 (en) |
| JP (1) | JPH08500771A (en) |
| KR (1) | KR950702877A (en) |
| CN (1) | CN1113075A (en) |
| AU (1) | AU687082B2 (en) |
| BR (1) | BR9405431A (en) |
| CA (1) | CA2142904A1 (en) |
| CO (1) | CO4410239A1 (en) |
| CZ (1) | CZ45995A3 (en) |
| HU (1) | HU214504B (en) |
| LV (1) | LV10933B (en) |
| MY (1) | MY111521A (en) |
| PE (1) | PE56294A1 (en) |
| PL (1) | PL178796B1 (en) |
| RU (1) | RU95106612A (en) |
| SK (1) | SK75694A3 (en) |
| TW (1) | TW340134B (en) |
| UY (1) | UY23792A1 (en) |
| WO (1) | WO1995000259A2 (en) |
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| CN102897777A (en) * | 2012-10-16 | 2013-01-30 | 昆山伟翰电子有限公司 | Method for removing adhesiveness of surface of silica gel product |
| CN102962183A (en) * | 2012-12-10 | 2013-03-13 | 昆山伟翰电子有限公司 | Organic silicon product surface oil-seal method |
| CN103524714A (en) * | 2008-08-27 | 2014-01-22 | Sika技术股份公司 | Silane/urea compound as heat-activatable curing agent for epoxide resin compositions |
| CN105050977A (en) * | 2012-11-30 | 2015-11-11 | 康宁股份有限公司 | Sulfide solid electrolyte material, lithium solid battery and method of preparing sulfide solid electrolyte material |
| CN105829258A (en) * | 2013-10-18 | 2016-08-03 | 康宁股份有限公司 | Methods And Apparatus Providing A Substrate And Protective Coating Thereon |
| TWI642541B (en) * | 2013-10-18 | 2018-12-01 | 日產化學工業股份有限公司 | Glass substrate with protective film |
| CN111225920A (en) * | 2017-10-16 | 2020-06-02 | 信越化学工业株式会社 | Urea-group-containing organopolysiloxane, method for producing urea-group-containing organopolysiloxane, and cosmetic |
| CN116472319A (en) * | 2020-09-21 | 2023-07-21 | 株式会社世可 | Compound for ultra-thin strength-enhancing coating agent and strength-enhancing coating agent comprising the same |
| CN117247234A (en) * | 2023-11-20 | 2023-12-19 | 宁波旗滨光伏科技有限公司 | Glass chemical thinning agent and application thereof |
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| US6363749B1 (en) | 1997-04-04 | 2002-04-02 | Degussa Ag | Process for manufacturing surface-sealed hollow glass containers |
| DE19839682A1 (en) | 1998-09-01 | 2000-03-02 | Degussa | Production of surface sealed, hollow glass containers, comprises coating with a composition containing an alkoxysilane and a water soluble or dispersible mixture of a polyol and a cross-linking agent. |
| JPWO2004072150A1 (en) * | 2003-02-12 | 2006-06-01 | 日本化薬株式会社 | Epoxy group-containing silicon compound and thermosetting resin composition |
| CA2614154C (en) * | 2005-07-07 | 2014-01-14 | Arkema Inc. | Method of strengthening a brittle oxide substrate with a weatherable coating |
| JP2009511290A (en) * | 2005-10-05 | 2009-03-19 | ダウ・コーニング・コーポレイション | Coated substrate and manufacturing method thereof |
| EP2136935A4 (en) * | 2007-02-27 | 2010-12-29 | Tarksol Internat L L C | A method of applying a non-voc coating |
| US9346709B2 (en) | 2011-05-05 | 2016-05-24 | Corning Incorporated | Glass with high frictive damage resistance |
| KR102041176B1 (en) * | 2011-12-29 | 2019-11-07 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | Cleanable articles and methods for making and using same |
| FR3028778B1 (en) * | 2014-11-26 | 2019-04-12 | Glass Surface Technology | PROCESS FOR PRODUCING A COATING LAYER OF THE INTERNAL SIDE OF A CONTAINER AND CONTAINER OBTAINED WITH SUCH A METHOD |
| JP2023129854A (en) * | 2022-03-07 | 2023-09-20 | 東洋ガラス株式会社 | Coated glass container and method for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4049861A (en) * | 1975-03-07 | 1977-09-20 | Minnesota Mining And Manufacturing Company | Abrasion resistant coatings |
| US4374879A (en) * | 1981-02-02 | 1983-02-22 | Celanese Corporation | Glass bottle coating composition made from a salt of a polyamine terminated polyepoxide adduct, an epoxy crosslinker, a reactive silane, a surfactant and a natural or synthetic wax |
| US4424392A (en) * | 1982-03-24 | 1984-01-03 | Union Carbide Corporation | Aldehyde containing hydrolyzable silanes |
| JPS59121138A (en) * | 1982-12-28 | 1984-07-13 | Sapporo Breweries Ltd | Coating agent for bottle with abrasion |
| US4758646A (en) * | 1987-03-10 | 1988-07-19 | General Electric Company | Curable hydrophilic silicone polyether polymer |
| JPH0335073A (en) * | 1989-07-03 | 1991-02-15 | T S B:Kk | Production of inorganic coating composition |
| IE75704B1 (en) * | 1990-08-30 | 1997-09-10 | Atochem North America Elf | Method and means for incorporating functionality into an article and the article so produced |
| US5210156A (en) * | 1991-08-22 | 1993-05-11 | Dow Corning Corporation | Stable, moisture-curable silicone pressure sensitive adhesives |
-
1994
- 1994-06-21 CZ CZ95459A patent/CZ45995A3/en unknown
- 1994-06-21 PL PL94307564A patent/PL178796B1/en unknown
- 1994-06-21 CA CA002142904A patent/CA2142904A1/en not_active Abandoned
- 1994-06-21 WO PCT/US1994/007034 patent/WO1995000259A2/en not_active Application Discontinuation
- 1994-06-21 MY MYPI94001600A patent/MY111521A/en unknown
- 1994-06-21 CN CN94190546A patent/CN1113075A/en active Pending
- 1994-06-21 UY UY23792A patent/UY23792A1/en unknown
- 1994-06-21 AU AU72493/94A patent/AU687082B2/en not_active Ceased
- 1994-06-21 BR BR9405431-2A patent/BR9405431A/en not_active Application Discontinuation
- 1994-06-21 PE PE1994244955A patent/PE56294A1/en not_active Application Discontinuation
- 1994-06-21 KR KR1019950700660A patent/KR950702877A/en not_active Application Discontinuation
- 1994-06-21 HU HU9500502A patent/HU214504B/en not_active IP Right Cessation
- 1994-06-21 SK SK756-94A patent/SK75694A3/en unknown
- 1994-06-21 JP JP7503063A patent/JPH08500771A/en active Pending
- 1994-06-21 RU RU95106612/25A patent/RU95106612A/en unknown
- 1994-06-21 CO CO94026880A patent/CO4410239A1/en unknown
- 1994-06-21 EP EP94921992A patent/EP0655953A4/en not_active Withdrawn
- 1994-07-15 TW TW083106470A patent/TW340134B/en active
-
1995
- 1995-02-21 LV LVP-95-35A patent/LV10933B/en unknown
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| CN103524714A (en) * | 2008-08-27 | 2014-01-22 | Sika技术股份公司 | Silane/urea compound as heat-activatable curing agent for epoxide resin compositions |
| CN103524714B (en) * | 2008-08-27 | 2016-04-06 | Sika技术股份公司 | As the silane compound/carbamide compound of the heat-activatable solidifying agent for composition epoxy resin |
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| CN102897777A (en) * | 2012-10-16 | 2013-01-30 | 昆山伟翰电子有限公司 | Method for removing adhesiveness of surface of silica gel product |
| CN105050977B (en) * | 2012-11-30 | 2018-10-19 | 康宁股份有限公司 | The strengthened glass container of delamination and resistant to damage |
| CN105050977A (en) * | 2012-11-30 | 2015-11-11 | 康宁股份有限公司 | Sulfide solid electrolyte material, lithium solid battery and method of preparing sulfide solid electrolyte material |
| CN102962183A (en) * | 2012-12-10 | 2013-03-13 | 昆山伟翰电子有限公司 | Organic silicon product surface oil-seal method |
| CN105829258A (en) * | 2013-10-18 | 2016-08-03 | 康宁股份有限公司 | Methods And Apparatus Providing A Substrate And Protective Coating Thereon |
| TWI642541B (en) * | 2013-10-18 | 2018-12-01 | 日產化學工業股份有限公司 | Glass substrate with protective film |
| CN111225920A (en) * | 2017-10-16 | 2020-06-02 | 信越化学工业株式会社 | Urea-group-containing organopolysiloxane, method for producing urea-group-containing organopolysiloxane, and cosmetic |
| CN111225920B (en) * | 2017-10-16 | 2023-06-06 | 信越化学工业株式会社 | Ureido-containing organopolysiloxane, method for producing ureido-containing organopolysiloxane, and cosmetic |
| CN116472319A (en) * | 2020-09-21 | 2023-07-21 | 株式会社世可 | Compound for ultra-thin strength-enhancing coating agent and strength-enhancing coating agent comprising the same |
| CN117247234A (en) * | 2023-11-20 | 2023-12-19 | 宁波旗滨光伏科技有限公司 | Glass chemical thinning agent and application thereof |
| CN117247234B (en) * | 2023-11-20 | 2024-03-05 | 宁波旗滨光伏科技有限公司 | Glass chemical thinning agent and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2142904A1 (en) | 1995-01-05 |
| PE56294A1 (en) | 1995-01-17 |
| SK75694A3 (en) | 1995-07-11 |
| WO1995000259A3 (en) | 1995-02-09 |
| WO1995000259A2 (en) | 1995-01-05 |
| AU7249394A (en) | 1995-01-17 |
| BR9405431A (en) | 1999-09-08 |
| CO4410239A1 (en) | 1997-01-09 |
| PL178796B1 (en) | 2000-06-30 |
| LV10933A (en) | 1995-12-20 |
| RU95106612A (en) | 1997-01-20 |
| HUT72234A (en) | 1996-04-29 |
| CZ45995A3 (en) | 1995-12-13 |
| EP0655953A1 (en) | 1995-06-07 |
| TW340134B (en) | 1998-09-11 |
| JPH08500771A (en) | 1996-01-30 |
| LV10933B (en) | 1996-08-20 |
| AU687082B2 (en) | 1998-02-19 |
| KR950702877A (en) | 1995-08-23 |
| HU9500502D0 (en) | 1995-04-28 |
| MY111521A (en) | 2000-07-31 |
| PL307564A1 (en) | 1995-05-29 |
| UY23792A1 (en) | 1994-12-20 |
| HU214504B (en) | 1998-03-30 |
| EP0655953A4 (en) | 1996-09-04 |
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