WO2015188833A1 - Composition de lave-glace solide et son utilisation - Google Patents

Composition de lave-glace solide et son utilisation Download PDF

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Publication number
WO2015188833A1
WO2015188833A1 PCT/DK2015/050157 DK2015050157W WO2015188833A1 WO 2015188833 A1 WO2015188833 A1 WO 2015188833A1 DK 2015050157 W DK2015050157 W DK 2015050157W WO 2015188833 A1 WO2015188833 A1 WO 2015188833A1
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WIPO (PCT)
Prior art keywords
windshield washer
solid
liquid
weight
composition
Prior art date
Application number
PCT/DK2015/050157
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English (en)
Inventor
Søren KEGNÆS
Thomas Rene Hyldekær JANSTRUP
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Danmarks Tekniske Universitet
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Publication of WO2015188833A1 publication Critical patent/WO2015188833A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/20—Antifreeze additives therefor, e.g. for radiator liquids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/266—Esters or carbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3272—Urea, guanidine or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/34—Organic compounds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22—Organic compounds, e.g. vitamins
    • C11D9/26—Organic compounds, e.g. vitamins containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22—Organic compounds, e.g. vitamins
    • C11D9/30—Organic compounds, e.g. vitamins containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22—Organic compounds, e.g. vitamins
    • C11D9/32—Organic compounds, e.g. vitamins containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/18—Glass; Plastics

Definitions

  • a solid windshield washer composition and the use thereof are provided.
  • the present invention relates to a solid antifreeze composition
  • a solid antifreeze composition comprising a first compound, wherein said first compound when dissolved in a liquid, is freeze resistant at minus 10°C and below.
  • the typical windshield washer used today comprises two compounds, namely a "small” alcohol and a water.
  • small alcohol is meant an alcohol with 1 to 4 carbon atoms.
  • An example of a typical windshield washer is 25-50% alcohol and water added up to 100%.
  • Ethanol is the most commonly used alcohol for windshield washers.
  • Other components than alcohol and water, which may possibly be present in a liquid windshield washer as known today, are soap and colourings.
  • Liquid windshield washers with a lower amount of alcohol, such as below 15% alcohol, are known today. However, the freezing point of such products is higher because of the less amount of alcohol present.
  • Windshield washers in tablet form which are meant to be dissolved before use, are known.
  • these known windshield washer solutions made from tablets are not freeze resistant. In colder climates, it is a demand from users that windshield washers are freeze resistant at low temperatures, such as minus temperatures of two digits, such that the windshield washer can be used in frosty weather, which typically is from November to February. Windshield washers should not freeze or form brash ice in cold weather, because the nozzle in the sprinkler system will then be blocked and in worse case frost damages may occur.
  • a solid windshield washer being freeze resistant at low temperatures when dissolved would be advantageous. Further, focus on the environment increases more and more, and thus focus on preparing windshields washers which have a less impaired impact on the environment, is desirable.
  • the windshield washers known today, both the liquid ones and the solid ones to be dissolved comprise compounds which are not beneficial for the environment, e.g. alcohols. For example in Denmark, the yearly emission of ethanol from windshield washers is estimated to be approximately 4,500 tons.
  • an object of the present invention relates to providing a solid windshield washer composition that solves the above mentioned problems of the prior art.
  • the present invention also provides a solid windshield washer composition with which the expenses to transport, storage and other logistics are reduced as compared to when using liquid antifreeze solutions.
  • the solid antifreeze composition also provides environmental savings in form of for example less CO2 emission, since transportation and other logistics of the product are reduced.
  • one aspect of the invention relates to a solid windshield washer composition
  • a solid windshield washer composition comprising a first compound, wherein said first compound when dissolved is freeze resistant at minus 10°C and below and wherein said first compound is selected from the group consisting of guanidinium salts, N-substituted
  • guanidinium salts glycine esters or a mixture thereof.
  • Another aspect of the present invention is to provide a liquid windshield washer composition comprising the solid windshield washer composition according to the present invention and a liquid.
  • Yet another aspect of the present invention is the use of the solid windshield washer composition according to the present invention for preparing a liquid windshield washer, wherein the solid windshield washer composition is mixed with a liquid.
  • Numerical ranges as used herein are intended to include every number and subset of numbers contained within that range, whether specifically disclosed or not. Further, these numerical ranges should be construed as providing support for a claim directed to any number or subset of numbers in that range. For example, a disclosure of from 1 to 10 should be construed as supporting a range of from 1 to 8, from 3 to 7, from 4 to 9, from 3.6 to 4.6, from 3.5 to 9.9, and so forth.
  • the term "freeze resistant" refers to a solution which at a given temperature does not freeze, i.e. make ice crystal, and does not form a precipitate.
  • freeze resistant is not to be compared with “melting” or “melting point”.
  • the melting point is the temperature when a compound in solid state begins to melt to a liquid state.
  • Freezing point is when the liquid solution begins to make ice crystals and thus becomes a solid.
  • the melting point and freezing point may be different from each other.
  • antifreeze does similar to "freeze resistant" refer to a condition where a composition, when dissolved in a liquid and thus being in liquid state, has not yet begun to freeze, i.e. not yet begun to create ice crystals, and no precipitate has been formed.
  • the terms “antifreeze” and “freeze resistant” are used interchangeably.
  • freeze refers to when a solution is partly or fully frozen, i.e. ice crystals have been formed in the solution or precipitate has been formed in the solution.
  • the invention in one aspect relates to a solid windshield washer composition
  • a solid windshield washer composition comprising a first compound, wherein said first compound when dissolved is freeze resistant at minus 10°C and below and wherein said first compound is selected from the group consisting of guanidinium salts, N-substituted
  • guanidinium salts glycine esters or a mixture thereof.
  • the solid windshield washer composition may for example be in the form of a powder, granulate, capsule or tablet.
  • the solid windshield washer composition is in the form of a tablet.
  • the solid windshield washer composition is in the form of a powder or granulate, in particular a granulate.
  • the solid windshield washer composition may be prepared in tablets having a predefined weight.
  • the weight and size of the tablets is not limited to any particular size, but may be any size. The size is dependent on the amount of liquid solution which is to be prepared. If for example the solid windshield washer composition is dissolved and used as a windshield washer, the tablets should be of a size, such that the tablets may be dissolved in 3, 4, or 5 litres of liquid and poured into the windshield washer tank of a car. In such case, the tablets preferably have a weight of 5-300 g, such as 10-200 g, preferably 12-150 g.
  • the solid windshield washer composition according to the present invention comprises a first compound which when dissolved is freeze resistant at minus 10°C and below, such as at minus 11°C and below, preferably at minus 12°C and below.
  • the first compound when dissolved is freeze resistant at minus 15°C and below.
  • the first compound when dissolved is freeze resistant at minus 16°C and below and in particular at minus 18°C.
  • the first compound according to the present invention is selected from:
  • guanidinium salts N-substituted guanidinium salts, glycine esters or a mixture thereof.
  • These compounds have unexpectantly been shown to have a good solubility and to be freeze resistant at very low temperatures, such as at temperatures at minus 10°C and below, and also below minus 15°C.
  • the inventors of the present invention have found out that these compounds in very low concentrations in a solution will ensure that the solution is freeze resistant. Thus, the compounds will not freeze or precipitate at low temperatures, but will remain dissolved and liquid. The compounds are therefore found to be useful in windshield washer compositions.
  • the first compound is one or more of guanidinium salts.
  • the guadinium salts may be selected from the group consisting of guanidinium chloride, guanidinium nitrate, guanidinium carbonate, guanidinium thiocyanate, guanidinium cyanate, guanidinium sulphate, guanidinium acetate.
  • the guanidinium salt is guadinium chloride.
  • Guanidinium chloride may also be termed as guanidine hydrochloride, and the two terms refer to the same compound. Guanidinium chloride and guanidine hydrochloride refer to the same compound, but is written with different
  • Guanidine is a solid compound of the formula HNC(NH2)2. Guanidine is a strong base in water and is known to be used in the production of plastic. Further, Guanidine is a product of protein metabolism and may therefore be found in the urine of humans. Guanidinium is the protonated guanidine and is a highly stable cation in aqueous solution. Guanidinium salts may be used in denaturation of proteins. For example, guanidinium chloride is one of the strongest denaturants used in studies of protein folding. In a 6 molar solution of guanidinium chloride all proteins will denaturate and their structure be lost and most of the proteins will be randomly coiled .
  • guanidinium salts are highly beneficial in depressing the freezing point of water and can thus be used in a windshield washer composition.
  • Guanidinium salts are solids and can therefore be present in a solid windshield washer composition having the benefit of taking up less space during storage and transportation.
  • guanidinium salts when dissolved will be freeze resistant at temperatures down to minus 18°C.
  • the present inventors have found out that very small amounts of guanidinium salts can be used in a solution and still obtain freeze resistance.
  • guanidinium salts have been shown to have a good solubility at very low temperatures. For example, it has been shown that guinidinium salts are highly soluble, even at temperatures below minus 15°C, down to minus 18°C.
  • a solution of 11 g guanidinium salt dissolved in water to a concentration of 11 g per litre will not freeze at temperatures of minus 10°C.
  • a solution comprising 17.1 g/L of a solid antifreeze composition comprising 65% guanidinium chloride (guanidine hydrochloride) and 34% sodium methoxide and 1% soap will not freeze at temperatures of minus 10°C.
  • g/L refers to the concentration of a compound in a solution.
  • a solution having a specific concentration of a compound is made by measuring the amount of a compound and then adding water up to 1 litre.
  • a solution having a guanidine hydrochloride concentration of 11 g/L is made by first weighing 11 g of guanidine hydrochloride and then addding water up to 1 litre.
  • Higher amounts of guanidinium chloride in a solution, such as 50 g/L will result in a solution which is freeze resistant at minus 15°C.
  • the first compound of the present invention is selected from N-substituted guanidinium salts.
  • the N-substituted guanidinium salt may for example be tetramethyl guanidine hydrochloride, l-(3-Phenylpropylamino) guanidine hydrochloride, Robenidine hydrochloride , l-(4-Nitrophenyl)guanidine hydrochloride, l-(2,4-Xylyl)guanidine carbonate or mixtures thereof.
  • N-substituted guanidinium salts have surprisingly been found to decrease the freezing point of water and can thus be used as in a windshield washer
  • N-substituted guanidinium salts such as tetramethylguanidine chloride in an amount of 85 g/L will result in a solution which is freeze resistant at minus 15°C, while a solution of 15 g/L tetramethylguanidine chloride will be freeze resistant at minus 12°C.
  • the N-substituted guanidinium salt is tetramethylguanidine hydrochloride.
  • the glycine esters are glycine ethyl ester hydrochloride.
  • the first compound is a glycine ethyl ester hydrochloride.
  • glycine derivates are known as de-icing agents, e.g. betaine.
  • glycine esters have unexpectedly been shown to have an improved anti-freeze effect than for example betaine and are freeze resistant at lower temperatures than betaine and in much smaller concentrations.
  • the glycine ester glycine ethyl ester hydrochloride is freeze resistant at -10°C in conctrations as low as 15 g/L.
  • the first compound is a mixture of
  • the first compound is a mixture of two or more of guanidinium salts,
  • the first compound is a mixture af guanidine hydrochloride and glycine ethyl ester hydrochloride.
  • the solid windshield washer composition should preferably comprise the first compound in an amount of at least 1% by weight, such as at least 3% by weight, preferably at least 5% by weight, such as at least 6% by weight, even more preferably at least 8% by weight.
  • the solid windshield washer composition comprises the first compound in an amount of at least 10% by weight, such as at least 20% by weight, preferably at least 30% by weight, such as at least 40% by weight, even more preferably at least 50% by weight.
  • the solid windshield washer composition comprises a low amount of the first compound, then a higher amount of the solid windshield wsher composition will need to be added to a liquid in order to decrease the freezing point and thus obtain freeze resistance. Further, the solubility of the solid windshield washer composition may be decreased if the composition comprises too much of another compound which is poorly dissolvable at low temperatures. Thus, all or most of the components in the solid windshield washer composition should be easily dissolved.
  • the solid windshield washer composition comprising the first compound in an amount of 1-100% by weight.
  • the solid windshield washer composition comprises the first compound in an amount of 5-95% by weight, such as 8-85% by weight, preferably 10-75% by weight, such as 15-70% by weight, even more preferably 20-60% by weight, such as 25-50% by weight, preferably 30-45% by weight.
  • the solid windshield washer composition may also in a preferred embodiment comprise a base.
  • Addition of the base may have several improved effects on the solid windshield washer composition, for example addition of a base will neutralize the pH of the composition, if the first compound used is acidic. Further, the base may improve the decrease of the freezing point of water and thus provide a synergistic effect with the first compound even when small amounts are added.
  • the base itself is not appropriate to use as the only freeze depressing agent because of the elevated pH in these solutions. Further, bases such as sodium methoxide has a poor solubility in water.
  • the base is selected form the group consisting of alkali hydroxides, alkaline earth hydroxides, alkali alkoxides, alkaline earth alkoxides, alkali carbonates, alkaline earth carbonates, alkali carbamates, alkaline earth carbamates, alkali bicarbonate and alkaline earth bicarbonate.
  • the alkali metals preferably used as the alkali hydroxides, alkali alkoxides, alkali carbonates, alkali carbamates and alkali bicarbonate is sodium and potassium .
  • alkaline earth metals preferably used as the alkaline earth hydroxides, alkaline earth alkoxides, alkaline earth carbonates, alkaline earth carbamates and alkaline earth bicarbonate is magnesium and calcium.
  • the alkoxides is preferably methoxides or ethoxides, and most preferably methoxides.
  • the base is selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, sodium methoxide, potassium methoxide, calcium methoxide, magnesium methoxide, sodium carbamate, potassium carbamate, calcium carbamate, magnesium carbamate, sodium bicarbonate, potassium bicarbonate, calcium bibarbonate and magnesium bicarbonate.
  • the base is preferably present in an amount of 0 to 90% by weight, preferably from 0 to 70% by weight, such as from 0 to 60% by weight, even more preferably from 0 to 50% by weight.
  • the base is present in an amount of less than 50% by weight of the solid windshield washer composition, such as less than 45% by weight, preferably less than 40% by weight of the solid windshield washer composition.
  • the solid windshield washer composition according to the present invention may also comprise ammonium carbamate, ammonium carbonate, ammonium bicarbonate or a mixture thereof. In a preferred
  • the solid antifreeze composition comprises ammonium carbamate.
  • the solid windshield washer composition according to the present invention may also comprise a soap.
  • a soap is preferably added when the solid windshield washer composition is used as a cleaning agent.
  • the inventors of the present invention believe that besides from providing a cleaning effect, the soap will also provide an improved antifreezing effect when the solid composition is dissolved in liquid, i.e. the solid windshield washer composition comprising a first compound according to the present invention and a soap will obtain a lower freezing point when dissolved in liquid than a solid windshield washer composition comprising only the first compound. The freezing point will be even further lowered if the solid antifreeze composition besides from comprising a first compound also comprises a soap and a base.
  • the solid windshield washer composition comprises from 1 to 100% by weight of a first component, from 0 to 5% by weight of a soap, and from 0 to 90% by weight of a base.
  • the solid windshield washer composition comprises both a first compound according to the present invention, a base and a soap.
  • the soap may be any soap suitable for washing and cleaning, and in particular soaps suitable for windshield washing.
  • the soap may for example be selected from the group of sulfonic acid sodium salts, such as sodium dodecyl sulphate or dodecylbenzenesulfonic acid sodium salt.
  • the soap is sodium dodecyl sulphate.
  • the solid windshield washer composition according to the present invention may also comprise ammonium formate and/or ammonium acetate. Ammonium formate evaporates completely as ammonia and formic acid, while ammonium acetate evaporates as ammonia and acetic acid. Thus, ammonium formate and
  • ammonium acetate will when used in a windshield washer not precipite and cause deposits on the windshield of a car. Furthermore, ammonium formate and ammonium acetate are highly soluble in water.
  • the solid windshield washer composition comprises ammonium formate. Ammonium formate and/or ammonium acetate may be used in amounts up to 95% by weight, preferably from 0 to 95% by weight, such as from 1 to 90% by weight.
  • the solid windshield washer composition will, according to the present invention when comprising a first compound and ammonium acetate and/or ammonium formate, have an improved antifreeze effect, since a synergistic antifreeze effect is obtained between the first compound and ammonium acetate and/or
  • the solid windshield washer composition may comprise further components such as colour agents, aroma agents, softeners, surfactants or a mixture thereof.
  • the solid antifreeze composition according to the present invention is not limited to a particular form or shape.
  • the solid composition may be in the form of for example a powder, granulate, capsule, or tablet.
  • a tablet or capsule may be preferable if the solid composition is used for preparing a liquid windshield washer or liquid cleaning agent, since a tablet or a capsule can be made with a specific weight such that the user using the solid antifreeze composition can easily dissolve a tablet or capsule in a specified amount of liquid.
  • the solid antifreeze composition may also be in the form of a powder or granulate.
  • a packet or container can contain a specific volume of the powder or granulate and said powder or granulate can bedissolved in liquid before use as a windshield washer.
  • the solid windshield washer composition is in the form of a tablet.
  • the solid antifreeze composition is in the form of a granulate. Liquid windshield washer composition
  • a further aspect of the invention relates to a liquid windshield washer composition
  • a liquid windshield washer composition comprising a solid windshield washer composition according to the invention and a liquid.
  • the solid windshield washer composition according to the invention is dissolved in a liquid and is then ready to be used as a windshield washer.
  • the liquid windshield washer composition comprises the solid windshield washer composition according to the present invention in an amount of at least 1.0% by weight of the liquid composition, such as at least 1.2% by weight, preferably at least 1.5% by weight, such as at least 1.7% by weight.
  • 1.0 to 10% by weight of the liquid composition such as 1.1 to 7% by weight, for example 1.2 to 5% by weight, such as 1.5 to 4% by weight of the liquid composition.
  • One of the benefits of the solid windshield washer composition according to the invention is that it is highly soluble at minus temperatures and has an antifreeze effect in low concentrations. It is onlynecessary to use a low amount of the solid windshield washer composition in the liquid windshield composition in order to obtain the antifreeze effect.
  • the solid windshield washer composition comprises the first compound in an amount of 10 to 150 g/L, such as 15 to 100 g/L, preferably 20 to 75 g/L, such as 50 to 130 g/L, for example 80-120 g/L.
  • the liquid windshield washer composition comprises the first compound in an amount of at least 10 g/L, such as at least 15 g/L, preferably at least 30 g/L, such as at least 40 g/L, preferably at least 50 g/L, even more preferably at least 80 g/L, such as at least 90 g/L, preferably at least 95 g/L.
  • the liquid is preferably water, but may be a combination of water and another suitable liquid, for example a combination of water and an alcohol. Alcohols used may for example be methanol, ethanol, propanol, butanol, pentanol,
  • propyleneglycol ethyleneglycol, glycerol or a mixture thereof.
  • Propanol may be 1-propanol or 2-propanol and butanol may be 1-butanol, 2- butanol or tert-butanol.
  • the alcohol is selected from the group of methanol, ethanol, 1-propanol or 2-propanol or a mixture thereof. It is preferred to have no or at least a low amount of alcohol present in the liquid windshield washer composition according to the invention, since one of the objects of the invention is to decrease the amount of alcohols left in the
  • liquid windshield washer composition is easy to prepare by dissolving the solid windshield washer composition just before use.
  • water alone and not alcohol is convenient to use. Alcohol in low amount may however be added in some embodiments of the invention.
  • the liquid windshield washer composition has a ratio between water and alcohol which is not above 10: 1, preferably not above 15: 1, such as not above 20: 1, more preferably not above 30: 1, such as not above 40: 1, even more preferably not above 50: 1, such as not above 60: 1 or not above 70: 1.
  • the liquid windshield washercomposition has a ratio between water and alcohol being from 10: 1 to 100: 1, such as from 20: 1 to 100: 1, preferably from 50: 1 to 100: 1.
  • the amount of alcohol in a liquid which is a mixture of water and alcohol is from 0 to 10% by weight of the liquid, such as from 0 to 5.0% by weight alcohol, preferably from 0.1 to 5.0% by weight alcohol, such as from 0.2 to 4.0% by weight alcohol, preferably from 0.3 to 3.0% by weight alcohol, such as from 0.4-2.0% by weight alcohol, such as from 0.5 to 1.0 % by weight alcohol.
  • no alcohol is present.
  • the solid windshield washer composition according to the present invention both has a very good solubility at low temperatures and is highly effective in
  • the ratio between the solid windshield washer composition and the liquid is at least 1: 100 by weight, such as at least 1 :90 by weight, 1 : 80 by weight, 1 : 70 by weight, 1 : 65 by weight.
  • the term "at least” in the context of defining a ratio, e.g. 1: 65, between "X" and “Y” mean that there may be at least 1 g "X” and 65 g "Y", such as for example there may be 5 g "X” and still 65 g "Y”.
  • the ratio between the solid windshield washer composition and the liquid is from 1 : 100 to 1 : 10 by weight, preferably from 1 :90 to 1 : 20 by weight, such as from 1 : 80 to 1 : 20 by weight, preferably from 1: 70 to 1 : 30 by weight, such as from 1 : 65 to 1 : 30 by weight.
  • the solid windshield washer composition according to the present invention may be used in preparing a liquid windshield washer composition, wherein the solid windshield washer composition is dissolved in a liquid, e.g. water, in an amount of from 1.0% to 20% by weight.
  • a liquid e.g. water
  • the solid windshield washer composition may in preferred embodiments be dissolved in water in amounts of from 1.2% to 15% by weight, such as from 1.5% to 10% by weight, preferably from 1.7% to 8% by weight.
  • the solid windshield washer composition may be used for the preparation of a liquid windshield washer where the solid windshield washer composition is mixed with a liquid, such as water or a mixture of water and alcohol.
  • the windshield washer composition may also preferably comprise a soap, a base, ammonium formate and/or ammonium acetate. Further, the composition may also comprise ammonium carbamate, ammonium carbonate, ammonium bicarbonate or a mixture thereof. The soap will improve the washing effect while the base improves the freezing depressant effect of the solid antifreeze composition.
  • the solid windshield washer composition according to the present invention is that it is easy and cheap to transport and store since it is in a solid form which may be dissolved before use. Thus, transportation and storage of the liquid is avoided.
  • the solid windshield washer composition according to the present invention is freeze resistant at temperatures below minus 10°C and is therefore suitable to be used during the winters in colder climates. No brash ice or precipitation is made with the windshield washer according to the present invention. A good cleaning effect is obtained.
  • the solid windshield washer composition does not enhance eroding or rusting of the surfaces of a car. Furthermore, rubber bands around glass surfaces of the car are not swelled by the composition of the invention.
  • the solid windshield washer composition comprises 1-100% by weight of a first compound, 0-5 % by weight soap, 0-90% by weight of a base and 0-95% by weight of ammonia formate, ammonia acetate, ammonium carbamate, ammonium carbonate, ammonium bicarbonate or a mixture thereof.
  • the solid windshield washer composition according to the present invention may be used as a windshield washer.
  • the solid windshield washer composition When used as a windshield washer, the solid windshield washer composition may either be poured directly into the tank of a car and water added to the tank, such that the liquid windshield washer composition is mixed directly in the tank of a car or the solid windshield washer composition and liquid is mixed outside the car and afterwards poured into the windshield washer tank of the car.
  • concentrations of solid components glycine ethyl ester hydrochloride and (NaOMe).
  • a standard solution having 2 g glycine ethyl ester hydrochloride and 0.77 g sodium methoxide was prepared and water was added up to 25 ml.
  • Table 2 shows freezing tests of a composition comprising glycine ethyl ester hydrochloride, sodium methoxide and soap dissolved in water for different concentrations of solid components.
  • a standard solution having 2 g glycine ethyl ester hydrochloride, 0.77 g sodium methoxide and 50 mg soap was prepared and water was added up to 25 ml.
  • tables 1 and 2 show that glycine ethyl ester hydrochloride decreases the freezing point of water, both when present alone and when present in a mixture of glycine ethyl ester hydrochloride and soap. Tables 1 and 2 also show that
  • table 3 is a freezing test of a composition comprising guanidine hydrochloride, sodium methoxide and soap dissolved in water shown for different concentrations of solid components (guanidine hydrochloride + NaOMe + soap).
  • a standard solution having 2 g tetramethyl guanidine hydrochloride, 712 mg sodium methoxide and 50 mg soap was prepared and water was added up to 25 ml.
  • 10 samples were prepared from the standard solution having different concentrations solid components. 2 ml of each of the 10 samples with different concentrations were placed in cooling baths with different temperatures; -10°C, - 12°C and -15°C and it was observed whether the samples after 18 hours storage were freeze resistant.
  • tables 3 and 4 show that guanidine hydrochloride and Me 4 GuaHCI decrease the freezing point of water, such that solutions comprising said will be freeze resistant at minus 12°C in very low concentrations. Further, it is shown from tables 3 and 4 that solutions comprising guanidine hydrochloride and/or
  • hydrochloride is freeze resistant at minus 18°C. Also, it can be seen from tables 3 and 4 that guanidine hydrochloride is more efficient as a freeze resistant component than Me 4 GuaHCI, since lower amounts of guanidine hydrochloride than of Me 4 GuaHCI can be used without the solution is frozen or a precipitate is formed.
  • table 5 is a freezing test of a composition comprising guanidine hydrochloride dissolved in water shown for different concentrations of guanidine hydrochloride. No additives added. A standard solution with 3 g guanidine hydrochloride and water added up to 25 ml was prepared. 10 samples were prepared from the standard solution having different concentrations of guanidine hydrochloride. 2 ml of each of the 10 samples were placed in cooling baths with different
  • table 5 shows that the use of guanidine hydrochloride decreases the freezing point of water.
  • Table 5 shows that solutions of guanidine hydrochloride are freeze resistant at minus 12°C in very low concentrations. Further, table 5 shows that solutions of guanidine hydrochloride is freeze resistant at minus 15°C in concentrations above 49.2 g/L, but not freeze resistant at minus 15°C when the concentration of the solution is 39.3 g/L or below. Also, table 5 shows that solutions of guanidine hydrochloride is freeze resistant at minus 18°C in concentrations above 90 g/L.
  • Freezing tests of a mixture of guanidine hydrochloride and glycine ethyl ester hydrochloride have been performed. Each sample was prepared by diluting a concentrated standard solution of guanidine hydrochloride, glycine ethyl ester hydrochloride and sodium methoxide (NaOMe) in water.
  • Table 6 shows a freezing test of a composition comprising guanidine
  • hydrochloride glycine ethyl ester hydrochloride, sodium methoxide and soap, dissolved in water for different concentrations of solid components.
  • a 25 ml standard solution was prepared comprising 1.0 g guanidine hydrochloride, 1.0 g glycine ethyl ester hydrochloride, 950 mg NaOMe and 50 mg soap.
  • the standard solution was diluted to different concentrations of solid components and 2 ml of each of the samples were placed in cooling baths with different temperatures; - 10°C, -12°C and -15°C and it was observed whether the samples after 18 hours storage were freeze resistant.
  • Table 6 shows that a combination of guanidine hydrochloride and glycine ethyl ester hydrochloride will be freeze restistant at very low temperatures.
  • Table 6 shows that solutions with a combination of guanidine hydrochloride and glycine ethyl ester hydrochloride are freeze resistant at minus 12°C in very low concentrations, such as down to at least 25.2 g/L.
  • table 6 shows that solutions of a combination of guanidine hydrochloride and glycine ethyl ester hydrochloride are freeze resistant at minus 15°C in concentrations above 96.0 g/L, but not freeze resistant when the concentration of the solution is 76.8 g/L or below.
  • Solution 1 0 g/L guanidine hydrochloride and 120 g/L ammonium formate.
  • Solution 2 4 g/L guanidine hydrochloride and 116 g/L ammonium formate.
  • Solution 3 8 g/L guanidine hydrochloride and 112 g/L ammonium formate.
  • Solution 4 16 g/L guanidine hydrochloride and 104 g/L ammonium formate.
  • Solution 5 32 g/L guanidine hydrochloride and 88 g/L ammonium formate.
  • Solution 6 64 g/L guanidine hydrochloride and 56 g/L ammonium formate.
  • concentrations of solid components The six standard solutions were diluted to different concentrations of solid components and 2 ml samples was placed in cooling baths at a temperature of - 15°C and it was observed whether the samples after 18 hours storage were freeze resistant.
  • Table 7 Freezing tests of solutions 1-3 (guanidine hydrochloride and ammonium formate), at -15°C.
  • Table 8 Freezing tests of solutions 4-6 (guanidine hydrochloride and ammonium formate), at -15°C.
  • Example 5 Example of a granulate for windshield washing
  • Table 9 shows an example of a solid windshield washer composition according to the invention, where the solid composition is in the form of a granulate.
  • Table 10 shows another example of a solid windshield washer composition according to the invention, where the solid composition is in the form of a powder.

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Abstract

La présente invention concerne une composition de lave-glace solide comprenant un premier composé, ladite composition de lave-glace solide dissoute dans un liquide étant résistante au gel à une température égale ou inférieure à moins 10 °C.
PCT/DK2015/050157 2014-06-10 2015-06-10 Composition de lave-glace solide et son utilisation WO2015188833A1 (fr)

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WO2017008810A1 (fr) * 2015-07-10 2017-01-19 Danmarks Tekniske Universitet Concentré pour lave-glace et son utilisation
KR20180054550A (ko) * 2018-05-16 2018-05-24 호서대학교 산학협력단 부동제 조성물 및 이를 이용한 염소계 화합물의 동결방지 방법

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GB1463401A (en) * 1974-02-13 1977-02-02 Morton Norwich Lab Ltd Anti-freeze compositions
US4502892A (en) * 1978-12-27 1985-03-05 Hoechst Aktiengesellschaft Method for cleaning a glass surface with solutions of dissolved pelleted components containing high molecular weight polyphosphates, carbonates and acid-forming substances
US5942150A (en) * 1995-08-17 1999-08-24 Bayer Aktiengesellschaft Use as antifreeze of polymers with recurring succinyl units
US6294104B1 (en) * 1997-08-29 2001-09-25 Fortum Power And Heat Oy Liquid for the prevention of freezing of aircrafts and runways
US20060293208A1 (en) * 2005-06-23 2006-12-28 Egbe Matthew I Composition for removal of residue comprising cationic salts and methods using same

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WO2017008810A1 (fr) * 2015-07-10 2017-01-19 Danmarks Tekniske Universitet Concentré pour lave-glace et son utilisation
KR20180054550A (ko) * 2018-05-16 2018-05-24 호서대학교 산학협력단 부동제 조성물 및 이를 이용한 염소계 화합물의 동결방지 방법
KR101967337B1 (ko) * 2018-05-16 2019-04-09 호서대학교 산학협력단 부동제 조성물 및 이를 이용한 염소계 화합물의 동결방지 방법

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