A solid windshield washer composition and the use thereof

Technical field of the invention

The present invention relates to 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.

Background of the invention

Products like windshield washers are normally liquid compositions which are stored and sold as liquid compositions and poured into the windshield washer tank of a car. The use of windshield washers worldwide is enormous; In Denmark alone, it is estimated that about 18 million litres of windshield washer is used every year.

The typical windshield washer used today comprises two compounds, namely a "small" alcohol and a water. By "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.

Liquid windshield washers take up a lot of space both under transportation and storage. Therefore, the storage and transport expenses with the currently know windshield washers are high. Windshield washers in tablet form which are meant to be dissolved before use, are known. However, 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.

Hence, 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.

Another problem with known windshield washers with a high amount of alcohol is that in frosty weather alcohol evaporates faster than water and thus easily leaves ice on the front window of the car if using the windshield washer while driving.

Hence, there is a need for a solid windshield washer composition which is not damaging to the environment or at least less damaging to the environment and which when dissolved and thus in liquid state, is freeze resistant at minus 10°C and below.

Summary of the invention

Thus, an object of the present invention relates to providing a solid windshield washer composition that solves the above mentioned problems of the prior art. In particular, it is an object of the present invention to provide a solid windshield washer composition which is less damaging to the environment than the products used today. Further, it is an object of the present invention to provide a solid windshield washer composition which has a less damaging effect on plants than known products. 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. As a consequence hereof, 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.

Further, it is an object of the present invention to provide a solid windshield washer composition which when dissolved is freeze resistant at minus 10°C and temperatures below, in particular at temperatures at minus 15°C and below.

Furthermore, it is an object of the invention to provide a solid windshield washer which when dissolved is freeze resistant in low concentrations such as from 1- 20% at minus 10°C and below, preferably at minus 15°C and below. Thus, one aspect of the invention relates to 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. The present invention will now be described in more detail in the following. Detailed description of the invention

Definitions

Prior to discussing the present invention in further details, the following terms and conventions will first be defined :

In the context of the present invention, mentioned percentages are weight/weight percentages unless otherwise stated. The term "and/or" used in the context of the "X and/or Y" should be interpreted as "X", or "Y", or "X and Y".

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. In the context of the present application, 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. When a solution is freeze resistant at a given temperature, it means that the solution is still in a liquid state, no ice crystals has been formed, such as no brash ice or slush ice, and no precipitate has been formed in the solution. In the context of the present invention, "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.

The term "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.

Contrary to "freeze resistant" and "antifreeze", the term "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.

All references to singular characteristics or limitations of the present invention shall include the corresponding plural characteristic or limitation, and vice versa, unless otherwise specified or clearly implied to the contrary by the context in which the references is made.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art.

Solid windshield washer composition

The invention in one aspect relates to 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. In a preferred embodiment, the solid windshield washer composition is in the form of a tablet. In another preferred embodiment, 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. In a particular preferred embodiment, the first compound when dissolved is freeze resistant at minus 15°C and below. In a further embodiment, 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.

In a preferred embodiment, 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.

In a preferred embodiment, 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

nomenclature. Often, neutral compounds which are brought to the cationic form changes their name such that they end with "ium".

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 . The inventors of the present invention has found out that 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. Further, guanidinium salts when dissolved will be freeze resistant at temperatures down to minus 18°C. Further, the present inventors have found out that very small amounts of guanidinium salts can be used in a solution and still obtain freeze resistance. Furthermore, 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.

The inventors of the present invention have found out that 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. Furthermore, 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.

The term "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. For example, 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.

In another preferred embodiment, 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.

The 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

composition. The inventors of the present invention has surprisingly found out that 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. In a particular embodiment of the invention, the N-substituted guanidinium salt is tetramethylguanidine hydrochloride.

In another embodiment of the invention, the glycine esters are glycine ethyl ester hydrochloride.

Thus, in a preferred embodiment of the invention, the first compound is a glycine ethyl ester hydrochloride.

Other glycine derivates are known as de-icing agents, e.g. betaine. However, 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. For example, the glycine ester glycine ethyl ester hydrochloride is freeze resistant at -10°C in conctrations as low as 15 g/L. In an embodiment of the invention, the first compound is a mixture of

compounds, such as a mixture comprising one or more of guanidinium salts, N- substituted guanidinium salts, and glycine esters. In a preferred embodiment, the first compound is a mixture of two or more of guanidinium salts,

tetramethylguanidine chloride, and glycine ethyl ester hydrochloride. In a particular embodiment, 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. In other embodiments of the invention, 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.

If 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.

One embodiment of the invention relates to the solid windshield washer composition comprising the first compound in an amount of 1-100% by weight. In a further embodiment, 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. In an embodiment of the invention, 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 .

The 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. Thus, in an embodiment of the invention, 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. In a particularly preferred embodiment, 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. In a further embodiment, 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

embodiment, 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. Without being bound by any theory, 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.

In an embodiment of the invention, 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.

Thus, in a preferred embodiment of the invention, 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. Preferably, 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. In a preferred embodiment, 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

ammonium formate.

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. However, 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. In a preferred embodiment, the solid windshield washer composition is in the form of a tablet. In another preferred embodiment, 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 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. For example in an amount of 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. Thus, in an embodiment of the invention, 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.

In another embodiment of the invention, 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. Most preferably, 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

environment. Further, the liquid windshield washer composition is easy to prepare by dissolving the solid windshield washer composition just before use. Thus, water alone and not alcohol is convenient to use. Alcohol in low amount may however be added in some embodiments of the invention.

In an embodiment 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.

In another embodiment of the invention, 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.

In another embodiment of the invention, 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. In a preferred embodiment, 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

decreasing the freezing point. Thus, even when the solid windshield washer composition is mixed with a liquid such as water, in very small amounts, it will be freeze resistant at low temperatures and at temperatures below minus 10 degrees. In an embodiment of the invention, 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. In the context of the present application, 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".

In a further embodiment, 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.

Use

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. 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.

One advantage of 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. Another advantage is that 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. In an embodiment 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. 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.

It should be noted that embodiments and features described in the context of one of the aspects of the present invention also apply to the other aspects of the invention.

The invention will now be described in further details in the following non-limiting examples.

Examples

Example 1 - Freezing tests of glycine ethyl ester hydrochloride

Different freezing tests of glycine ethyl ester hydrochloride have been performed. Each sample was prepared by diluting a concentrated standard solution of glycine ethyl ester hydrochloride and sodium methoxide (NaOMe) in water. Table 1 shows freezing tests of a composition comprising glycine ethyl ester hydrochloride and sodium methoxide dissolved in water for different

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. 10 samples were prepared having different concentrations of glycine ethyl ester hydrochloride by diluting the standard solution. 2 ml of each of the 10 samples with different concentrations were placed in cooling baths with different temperatures;

-8°C, -10°C and -12°C and it was observed whether the samples after 18 hours storage were freeze resistant.

"+" refers to that the sample is liquid and no precipitate has been formed "-" refers to that the sample is either fully or partly frozen or a precipitate has been formed

Table 1 : 2.0 g glycine ethyl ester hydrochloride + 0.77 g NaOMe in 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. 10 samples were prepared having different concentrations of solid components by diluting the standard solution. 2 ml of each of the 10 samples were placed in cooling baths with different temperatures; -8°C, -10°C and -12°C and it was observed whether the samples after 18 hours storage were freeze resistant.

5 "+" refers to that the sample is liquid and no precipitate has been formed

"-" refers to that the sample is either fully or partly frozen or a precipitate has been formed

Table 2: 2.0 g glycine ethyl ester hydrochloride + 0.77 g NaOMe + 50 mg soap in 10 25 ml

Thus, 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

15 solutions of glycine ethyl ester hydrochloride is freeze resistant at minus 10°C and that freeze resistance is obtained with very low amounts of glycine ethyl ester hydrochloride. Example 2 - Freezing tests of guanidines

Different freezing tests of guanidine hydrochloride have been performed.

In 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 guanidine hydrochloride, 1.13 g 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 of solid components. 2 ml of each of the 10 samples were placed in cooling baths with different temperatures;

-10°C, -12°C, -15°C and -18°C and it was observed whether the samples after 18 hours storage are freeze resistant.

"+" refers to that the sample is liquid and no precipitate has been formed "-" refers to that the sample is either fully or partly frozen or a precipitate has been formed

Table 3: 2.0 g guanidine hydrochloride + 1.13 g NaOMe + 50 mg soap in 25 ml

Sample Amount solid -10°C -12°C -15°C -18°C components

(g/L)

11 127.2 + + + +

21 101.8 + + + +

31 81.4 + + + -

41 65.1 + + + -

51 52.1 + + + -

61 41.7 + + - -

71 33.4 + + - -

81 26.7 + + - -

91 21.3 + + - -

101 17.1 + + - - In table 4 is a freezing test of a composition comprising tetramethyl guanidine hydrochloride (Me ₄ GuaHCI), sodium methoxide and soap dissolved in water shown for different concentrations of solid components.

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.

"+" refers to that the sample is liquid and no precipitate has been formed

"-" refers to that the sample is either fully or partly frozen or a precipitate has been formed Table 4: 2.0 g Me ₄ GuaHCI + 712mg NaOMe + soap in 25 ml

Thus, 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

Me ₄ GuaHCI is freeze resistant at minus 15°C. Furthermore, guanidine

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. In 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

temperatures; -10°C, -12°C, -15°C and -18°C and it was observed whether the samples after 18 hours storage were freeze resistant.

"+" refers to that the sample is liquid and no precipitate has been formed

"-" refers to that the sample is either fully or partly frozen or a precipitate has been formed

Table 5: 3.0 g guanidine hydrochloride in 25 ml

Thus, 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.

Example 3 - Freezing tests of guanidine hydrochloride and glycine ethyl ester hydrochloride

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.

"+" refers to that the sample is liquid and no precipitate has been formed

"-" refers to that the sample is either fully or partly frozen or a precipitate has been formed

Table 6: 1.0 g guanidine hydrochloride + 1.0 glycine ethyl ester hydrochloride +

950mg NaOMe + 50 mg soap in 25 ml

Sample Amount solid -10°C -12°C -15°C

components

(g/L)

1J 120.0 + + +

2J 96.0 + + +

3J 76.8 + + - Sample Amount solid -10°C -12°C -15°C components

(g/L)

4J 61.4 + + -

5J 49.2 + + -

6J 39.3 + + -

7J 31.5 + + -

8J 25.2 + + -

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. Further, 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.

Example 4 - Freezing test of guanidine hydrochloride and ammonium formate

Freesing tests of a mixture of guanidine hydrochloride and ammonium formate has been performed.

Six different solutions has benn made having diffent ratios between guanidine hydrochloride and ammonium formate. The content of the solutions are mentioned 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.

In addition, all solutions comprises 50 mg sodium dodecylsulphate. Tables 7 and 8 show freezing tests of the solutions 1-6 comprising guanidine hydrochloride and ammonium formate, dissolved in water to different

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.

"+" refers to that the smaple is liquid and no precipitate has been formed

"-" refers to that the sample is either fully or partly frozen or a precipitate has been formed.

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.

Sample Solution 4 Solution 5 Solution 6

(16g GuaHCI) (32g GuaHCI) (64g GuaHCI)

g/L g/L g/L

IV + 122 + 122 + 122

2V + 98.6 + 98.6 + 98.6

3V + 78.9 + 78.9 + 78.9 Sample Solution 4 Solution 5 Solution 6

(16g GuaHCI) (32g GuaHCI) (64g GuaHCI)

g/L g/L g/L

4V + 63.1 + 63.1 + 63.1

5V + 50.5 + 50.5 + 50.5

6V - 40.4 - 40.4 - 40.4

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 9:

Compound Amount (g)

Guanidine hydrochloride 61.4

NH ₄ HC0 ₃ 4.78

(NH ₄ ) ₂ C0 ₃ 0.3

Soap 1.0

Bromthymolblue 0.003

Total weight 67.5

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.

Tabel 10:

Compound Amount (g)

Guanidine hydrochloride 30.2

Ammonium formate 7.2

Sodium methoxide 5.0

Soap 1.5

Bromthymolblue 0.003

Total weight 43.9