DE1467809A1 - Use of organic phosphate esters to prevent dental caries - Google Patents

Description

Patentem ** ff ^ ^^^ H67809

LEOSCHMCTZ 0IPL-MG-IRUNOSCHMiTZ AACHEN

Heinrichsallee 2 at Koiseralatz Fernspr. ff§

THE COIONIAI SUGAR HBFINING COMPANY IBIITBD, Sydney, New South. Wales (Australia.)

Patent application

Use of organic phosphate esters to prevent dental caries

The invention relates to the use of products that are suitable for dental care because they have the effect of Foods that cause tooth decay on the teeth and prevent wear and tear on the teeth. Dental care products according to the invention contain organic phosphates that are soluble, non-toxic and edible and can be incorporated into carriers.

The effect and influence of dental caries is already known Various known. The main factors are:

1. Bacteria that produce acids (for example of the lactic acid bacillus type, which form lactic acid) lie in the iuundhöhle in a larger view! before when dental caries infestation occurs.

2. Carbohydrates provide a favorable substrate for the formation of acids in the oral cavity. "With the designation" cariogenic " Food is hereinafter referred to as food, which consist of or contain carbohydrates.

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3. Acids that develop in the oral cavity take effect Tooth components and loosen them, making the teeth more susceptible to dental caries and tooth wear.

4. Prevent solutions containing calcium and phosphate in dissolved form an acid attack and also harden human tooth enamel that has been softened by acids. Fluoride accelerates the re-hardening.

The cariogenic effect of these acids arises from direct and usually longer contact between acid and tooth, Experts do not yet agree on the exact nature of the effect, but it is known that the acids in the dog or cause softening and erosion of tooth enamel in vitro. The softening or destruction of tooth enamel the dental caries follows.

It is also known that the cariogenic effects of these acids are due to the presence of certain soluble organic acids Phosphates such as sodium or ammonium phosphate is prevented. This cariostatic effect takes place in the dog or in vitro, however, the process is not yet fully understood.

Because of its local effect, the phosphate inhibitor should be present at the same time as and in the same place as the kario, ₅ new remedy. The cariogenic effect of acids mu; 3 he .I- Zm- surface take place in the mouth, and z v / ar on the never '' parts, an 'he acid touches the tooth Hence dan k ^ should riot;. ;; tati cixe Agents are present on the tooth surface.

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It would be ideal if the cariostatic agent in food, in particular carbohydrates, which tend to form cariogenic agents in the customer. Only in this ideal case the cariostatic shaker is definitely at the right time in the proper position to produce the most effective result. The cariostatic agent also works in dental care products and other carriers as described below.

Since it is desirable to introduce the active ingredient in food, For practical reasons, almost all or even all previously known cariostatic remedies are unsuitable. Soluble Have phosphates such as catalytic, ammonium or magnesium phosphates a very strong peculiar taste which, in effective concentrations of phosphate, gives food its own taste Adversely Affected Fluorides have known cariostatic properties, but are generally toxic and theirs Application in food requires constant and careful monitoring. Adding fluorine to the drinking water negligible quantities have not become generally accepted, Nevertheless, the reduction in dental caries is proven because the fluorides are toxic. Stable calcium phosphates might work under certain conditions, but are generally only sparingly soluble and like sodium phosphate a strong taste. These two properties prevent the ex-successful application of calcium phosphate in Food.

It has now been found that effective cariostatic phosphates

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or calcium or "both in the form of a soluble organic Compound that is non-toxic and has an insignificant taste can be applied. It is about it a product that can be incorporated into carbohydrate foods, beverages and other carriers without affecting the taste or other properties are affected while a substantial cariostatic effect is achieved.

According to the invention one uses certain non-toxic organic phosphates, in particular organic calcium phosphate, which the cariogenic effects of the acids formed in the dog or neutralize impede.

The cariostatic effect of the phosphates according to the invention is apparently based on a chemical action on the cariogenic substances in the mouth. The active ingredient according to the invention can therefore be found in tooth powders, mouthwashes, toothpastes and even in foods or condiments such as salt. The cariostatic agents are not as effective in dentifrices or the like as in food or drink, they However, due to their negligible toxicity, solubility and the lack of big taste in candy, Dental care products, mouthwashes and seasonings are available.

It has been found that phosphate esters obtained from organic compounds having hydroxyl groups or their Derivatives or salts are suitable cariostatic agents. Hydroxyl group-containing organic compounds from which such phosphate esters by partially or completely

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esterification of the hydroxyl groups are obtained are polyvalent Alcohols, cyclites, sugars, mono-, oligo- or polysaccharides and their derivatives.

Various of these phosphate esters or their derivatives or salts can be used in foods and / or dentifrices, beverages, prophylactic tablets, sweets or lozenges are entered and prevent the users from wearing out their teeth or dental caries.

In order to determine the cariostatic effect of the organic phosphate esters, the applicant has carried out extensive tests. It was found that different of the suitable active ingredients have different degrees of effectiveness with respect to their have cariostatic properties. The cariostatic effectiveness also depends on the concentration of the compound used away.

It has further been found that the calcium salt of the phosphate ester obtained from sucrose is particularly effective in reducing of gravel infestation in experimental animals. The sodium and sodium salts of sucrose phosphate esters are also cariostatic Effectiveness, which is, however, lower than that of the calcium salt and their taste properties are not so particularly beneficial.

The calcium, sodium, and magnesium salts of phosphate esters of sugars other than glucose and lactose also have, as tests have shown, cariostatic activity, but are

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not as effective as sucrose phosphate in general Concentrations.

Among the phosphate esters from polyhydric alcohols showed the calcium, sodium and magnesium salts of glycerol phosphateeter a cariostatic activity but not as great as that of calcium sucrose phosphate in similar Concentrations.

The phosphate esters and their derivatives or salts from the group of the compounds listed above have special requirements suffice if they are to serve as cariostatic agents. These conditions limit the number of the present invention suitable connections very considerably. The conditions are as follows:

1. They must have a cariostatic effect.

2. They have to be non-toxic.

3. They must be soluble.

4. They must be edible or tasteless.

5. They must be compatible with food, especially carbohydrates.

6. They have to be relatively cheap.

It should be noted that the conditions for 2, Z-, 4, and 6 relate to concentrations, you explained. are to meet condition 1.

Investigations of various of these substances, in particular of calcium sucrose phosphate, are explained in the following examples: _. _Λ

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Example A:

The oalsium salt of sucrose phosphate (Ca 0ΐ2Η2ΐ0ΐ4Ρ · 2Η ₂ 0) (a non-toxic, water-soluble white powder with a mild taste) prevented the corrosive effect of lactic acid on human tooth enamel in a test medium in vitro at a concentration of 0.5 # pH of only 3.8. On a weight basis, calcium carbonate phosphate is as effective as sodium phosphate (Na2HPO ^) which means it is three times as effective on a molar basis as sodium phosphate in preventing lactic acid from attacking tooth enamel.

Example B:

A strain of Osborn-Mendel rats with tooth decay occurs when following a high-carbohydrate diet fed has been shown to reduce the effectiveness of various salts of various organic phosphates the occurrence of caries when added in varying concentrations studied on the diet. The following is an example of the nature of the results obtained from such an experiment given:

The basic diet of the animals under consideration consisted of sugar (sucrose) 59 parts by weight

Skimmed milk powder 27 ""

Whole wheat flour 6 ""

Alpha 3 ""

Liver powder (from ox) 4 ""

None of the components of the diet contained significant amounts

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Fluoride. When a control group of rats from the Osborn-Mendel strain was treated for 6 weeks with this diet the animals tooth decay. Control groups were used in each series of experiments.

The basic diet with additive was given to the experimental groups of animals of varying proportions of salts of organic phosphate esters, which were well mixed with the dry food, given. The degree of dental caries in rats can be expressed in 2 different ways:

1. Number of rotten teeth regardless of the degree of injury.

2. Number and degree of injuries.

The results of 2 test series (each with its own control group) are given below, with the addition of Calcium sucrose phosphate was added to the basic diet in the specified amounts.

Addition to the diet % reduction in % reduction in

Number of caries Caries degrees in

affected teeth compared to the control

VgI. to the control group

0.5 # calcium sucrose- _Ar . _{of CI} _ _0}

phosphate ⁴⁰ * ⁵⁵ #

l, 0 # calcium _{sucrose- ΟΊ} . ,, _or . _rf

phosphate ⁸¹ ^ ⁸⁹ *

6.0% calcium sucrose- _Q , _Λ _. ^

phosphate ^bl * ⁸⁴ ^

The advantage of using cariostatic agents according to Invention compared to inorganic phosphates and fluorides as agents for reducing the incidence of dental caries and

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Tooth decay when added to food is due to the following!

1. Certain salts of the listed organic esters of phosphoric acid are suitable means of obtaining stable, soluble forms of phosphates and metals such as calcium contained in Form of inorganic phosphates are hardly soluble.

2. In contrast to inorganic fluorides are those according to the invention organic esters and their salts are not toxic. Some of them even make valuable food ingredients which can be supplied in an easily soluble form and provide sugar, phosphate and calcium or other metals, all of which are animal metabolic products.

3. In contrast to inorganic phosphates, the inventive Organic esters and their salts have a not unpleasant mild taste and influence the concentrations beyond what is necessary for maximum cariostatic effect the taste of food is not essential.

4 * Due to the properties listed above, the Esters according to the invention and their salts within, a broad Concentration range within which they are effective for combating dental caries and tooth wear v / ground (without affecting the taste or toxicity of the food).

5. You can also use mouthwashes or compositions for. Heinigen of teeth are added, in which their solubility Non-toxicity, the mild taste and the protective effect on the enamel against inorganic phosphates and fluorides gives a benefit.

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6. They can also be incorporated into prophylactic tablets or lozenges, especially for travelers and such users are suitable who do not use the cariostatic agents in the form according to points 4 and 5 above can use or to whom the funds are not available in this form.

It is known that carbohydrates have a cariogenic effect. According to a preferred feature of the invention, the cariostatic organic phosphate esters and / or their salts are used as an additive to foods and beverages containing carbohydrates. The esters and their salts can be found directly in sugar, flour and grain products such as rye, wheat, rice, oats, barley, and soy different mixtures such as bread and cake flours can be entered. If you use products to manufacture finished goods such as Bread or cake, then the finished product has a table top Effect without its taste or other properties being noticeably changed. You cariostatic ester and their salts can also be used directly in baked goods or cakes, confectionery, sugar confectionery, drinks, syrup, canned food, ice cream, Gelatin or the like. Be entered. Plant-based foods high in carbohydrates such as potatoes can be used with the cariostatic esters and salts can be cooked or the kster or their salts can be added to table salt or other flavorings and can only be used at the table.

The organic phos used according to the invention _; hatestev and their derivatives and salts can be used together with food in any V / eise, whereby it is ensured

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must that their distribution in foods is as even as possible.

The concentrations preferred for the inventive use of the salts of organic phosphate esters in foods are in the range between 0.1 to 6 wt.% Of the food. Higher concentrations in the foods consumed as part of the normal diet are not required to achieve the desired protection against tooth decay.

In mouthwashes and the like and in pharmaceutical compositions such as tablets or lozenges which are used prophylactically (and that are not direct dentifrices or foods) higher concentrations can also be used.

The maximum effectiveness of the additives according to the invention in organic Phosphate esters are formed when they are introduced into foods that mainly contain carbohydrates.

The salts of organic phosphates can be with the food or other ingredients are added during processing either as a solid or in solution. You can use the raw materials for food production or the finished product.

The invention is illustrated in the following examples:

example 1

Sugar: Sugar crystals are made with calcium sucrose phosphate

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overdrawn. A product is obtained with a content of 1 wt.% CalciumsaccharosephoBphat. The desired goal can be achieved in various ways, for example:

1. By spraying a solution of calcium sucrose phosphate in water onto present in a revolving dryer Sugar crystals.

2. By spraying on an aqueous solution of oaloium sucrose phosphate on the crystals before they are removed from the centrifuge during sugar production.

3. By mixing dry sugar and dry calcium sucrose phoephate in the presence of finely divided water spray.

Example 2

Flour: In a device for mixing dry matter is 1 wt. ^ Powdered calcium sucrose phosphate mixed with flour.

Example 3

Cereal products: A breakfast product made from so-called corn flakes is sprayed with a solution of calcium sucrose phosphate in water. The flakes are then dried to obtain a finished product containing 1 % calcium saccharose phosphate.

Example 4

Bread: 2 wt. $ Calcium sucrose phosphate are added to the flour when mixed of the ingredients for bread-making.

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Example 5

Cake mixϊ 1% by weight calcium sucrose phosphate is added to the Added drying agents for the cake mix.

Example 6

Liquid sugar: A liquid sugar is made, consisting of

Sucrose - 65% by weight

Calcium sucrose phosphate 0.5 wt. #

Water 34.5 G-ew. ^

Example 7

Confectionery division: When making a candy mix 2% by weight of calcium aceharose phosphate added to the sugar.

Example 8

Sponge cake: When making a sponge cake mix, the other dry ingredients 2 wt. # calcium sucrose phosphate added during mixing.

■ example 9

Beverages: Made from liquid sugar, in which 1% by weight calcium sucrose ^ phosphate is dissolved, a drink is made.

'Zi CO OO

Example lü

4 ^ Tablets: üb is a tablet with a content of 10 wt # • -J calcium phosphate and sucrose Trägeretoffen such as sugar, flavoring.

materials and binders produced · -.

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The karioatatiachen means used according to the invention are special effective in carbohydrate foods that are cariogenic or when exposed to acids and usually bacteria found in the mouth become cariogenic.

The formation of cariogenic substances such as i-lactic acid and the effect The lactic acid on the teeth apparently requires a certain amount Time. In order to achieve an optimal effect, the cariostatic Agents according to the invention are present when the cariogenic substances (acids) are formed, so that their inhibiting effect coincides with the cariogenic effect. Hence the application of the cariostatic compounds according to the invention in dentifrices, mouthwashes, prophylactic lozenges or Like. Appropriate.

In the production of dentifrices with the inventive Additives are the required salts of the selected organic phosphate esters in the dentifrice to appropriate Registered way, depending on whether a powder, a paste or a liquid composition is to be prepared. To this The purpose is to change appropriately suitable compositions of surfactants, binders, flavorings Support materials, which are necessary for the formation of the desired shape, are added.

The type and concentration of the salts of the verweu'.eto- *, Mniiid.o phosphate esters depends on the type of additive desired :. '.. _u sno .-; t ~ uni; of the product to be manufactured. The solubilities of the various salts or the organic phosphate esters vary

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considerably. For example, the calcium salt is sucrose phosphate Easily soluble in water, while dicalcium acetic acid diphosphate and calcium glycerol phosphate are hardly soluble.

The proportions of the various salts of the organic phosphate esters are generally chosen so that no less than 1 % of the salt is dissolved in the composition at a preferred concentration. The amount of insoluble salt used in the compositions can be up to 100 % depending on the nature of the composition and any other abrasives present. It should be noted that these relative concentrations of dissolved and undissolved salts may be achieved with a single salt of an organic phosphate ester.

The addition of certain fluorides in a suitable form to dental care products or mouthwashes with a content of cariostatic Organic phosphate esters or their salts can increase the effect of the cariostatic agent.

Example 11

Toothpaste: A toothpaste of the following composition is made:

Calcium sucrose phosphate 5

Tragacanth gum 1 weight> &

Saccharin (soluble) 0.1 Gevi.fo

Glycerine (organic, pure) 20.0 wt. #

Sodium lauryl sulfate 1.0 wt / 6

Methyl p-hydroxybenzoate 0.1 wt. 5 "

Flavor and color 1.0 wt / o

dibasic calcium phosphate 35.0 wt. %

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The powdery gum tragacanth, methyl p-hydroxybenzoate, flavoring agent and dye are dispersed in the glycerin. Saccharin and sodium lauryl sulphate are found in part of the water and calcium sucrose phosphate dissolved, the aqueous solution added to the glycerol dispersion and mixed well. To this mixture the calcium phosphate previously moistened with the remaining water is then added with thorough mixing.

Example 12

Toothpaste: A composition is prepared as in Example 11 and 2 % sodium fluoride is added in a suitable form.

Example 13

Toothpaste: A composition is prepared as in Example 11, but 0.4 % tin (II) fluoride is added in a suitable form.

Example 14

Toothpaste: A composition is prepared as in Example 11, however, like all dibasic calcium phosphate replaced by dicalcium sucrose diphosphate.

Example 15

Toothpaste: A composition as in Example 11 is produced, but 50 % of the dibasic calcium phosphate is replaced by dicalcium sucrose diphosphate.

Example 16

Tooth powder: The following composition is made:

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Calcium sucrose phosphate 5.0% by weight

soluble saccharin 0.1% by weight

Dye traces

dibasic calcium phosphate 94.9% by weight.

Example 17

Tooth powder: A composition is prepared as in Example 16, however, 1 # sodium fluoride is added in a suitable form.

Example 18

Tooth powder: The following composition is made:

Dye traces

soluble saccharin 0.1% by weight

Flavors traces

Dicalcium acetic acid dipho-sphat 99.9 wt. #

Example 19

Tooth powder: A composition is produced as in the example, but containing 5.0% by weight of calcium sucrose phosphate.

'hillt.

Example 20 '·.

Liquid dentifrice: a composition is made the end

Sodium alginate 1.5 wt. #

jicalcium sucrose diphosphate 5.0 wt. / o

Sodium Lauryl Sulphate 1.0 wt. #

Calcium sacchar sephosphate ^, 0 wt. I ^

Flavor traces

Dye traces

water 87.5% by weight

The pH is adjusted to 6.

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Coloring and flavoring substances are added to the diphosphate, the together with the alginate in the one containing the lauryl sulfate Water is dispersed. Calcium sucrose phosphate is added and the dispersion to the desired volume with Y / ater filled up. The pH value is then correct.

Example 21

Liquid dentifrice: A composition is prepared as in Example 20, but 0.5 i »sodium fluoride added.

As already stated, the invention is only illustrated by the above examples. There are numerous others as well Combinations possible. The invention relates in particular to the use with carbohydrates such as bread, bread ingredients, cakes,

Potatoes and the like. As well as with such foods that only develop low percentages of cariogenic carbohydrates such as breaded meat.

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Claims (7)

Claims 1. The use of soluble, non-toxic, organic phosphate esters and / or their salts, which have a mild taste, to prevent dental caries and tooth wear. 2. The method according to claim 1, characterized in that the phosphate ester used or its Salt was obtained from polybasic alcohols, cyclites or sugars, mono-, oligo- or polysaccharides or their derivatives, 3. The method according to claims 1 and 2, characterized in that that one uses the calcium salt of sucrose phosphate, glucose phosphate, lactose phosphate or glycerol phosphate or the corresponding sodium salts or magnesium salts are used. 4. Process according to Claims 1 to 3 »characterized in that that the phosphate esters are used together with cariogenic foods or in dental care products, mouthwashes, Using lozenges or drinks. 5. Process according to Claims 1 to 4, characterized in that that 0.1 to 6 wt .; of the cariostatic gown clogs. 6. The method according to claims 1 to 4, characterized in that that more than 1.0 Gev /. ^ o of the cariostatic oil is added to dental care products. 909836 / U77 - 20 - H67809 7. The method according to claims 1 to 4, characterized in that that one adds more than 1.0 Gew.ii of the carious LdLt-CeIs to mouthwashes and tablets. Aachen, July 7, 1962 For ΤΗΞ OOLOFIAL SU&AR HI5FININ & COIdPAIiY LIMISED The patent attorneys
by: (Dipl ^ ing. Bruno Schae-t ») 909836/1477