DE2327141A1 - SCAFFOLDING MATERIALS FOR DETERGENTS AND DETERGENTS - Google Patents

Description

KNAPSACK AKTIENGESELLSCHAFT _. 4 O 4 / i ¹ M

Builders for detergents and cleaning agents

The invention relates to builders for detergents and cleaning agents, consisting of copolymers of α-hydroxiacrylic acid and acrylic acid or its water-soluble salts.

It is known that the detergency of soaps and synthetic Detergents in detergents and cleaning agents is increased by adding certain water-softening products. Such Detergent enhancers are referred to as builders or "builders". Detergents and cleaning agents containing builders are more effective and yet cheaper than the corresponding builder-free formulations.

In supplements of the nonionic surfactant component one Detergent formulation that only disperses and / or peptises hydrophobic dirt, such as soot and fat particles, A detergent must also contain a component that is suitable for removing hydrophilic soil. This is the job of the builder or scaffold substances. In the absence With such a builder, the incrustation of dirt loosening from the tissue during the washing process is only incomplete absorbed by the washing liquor, so that it comes to the deposition of dirt particles on the laundry and no satisfactory washing effect is achieved.

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The mechanism and details of the "builder effect" are not yet fully clarified. There are several processes that play a role in the functioning of the builder, such as the stabilization of pigment dirt suspensions, the emulsification of dirt particles, the influencing of the surface and Interface properties of aqueous surfactant solutions that, solubilization of water-insoluble components of the cleaning liquor, the peptization of dirt agglomerates, the neutralization of acidic substances and the inactivation of Minerals in the wash liquor.

In order to obtain information about the performance and the suitability of individual products as builders, one expediently investigates in addition to their ability to bind Ca ions and their ability to form stable dispersions, also theirs Behavior and its efficiency when washing or Cleaning process. This ensures that all factors involved in the builder effect are qualitative and quantitative Find consideration.

Conventional builders are the water-soluble alkali salts of mineral acids, such as alkali carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates.

Of the numerous products proposed as Builder-Be in the usual detergents and cleaning agents almost exclusively the linear condensed alkali metal phosphates, in particular the sodium tripolyphosphate, used. The salary of the Detergents and cleaning agents on these builders is up to about 50% by weight.

As a result of the considerable increase in the consumption of phosphate-containing waxes and cleaning agents, both in households and in business has also increased the content of natural waters in these areas

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Phosphates increased. In the discussion about the causes of the increasing water eutrophication recently the water-soluble ones have been mentioned Nitrate and phosphate salts have the property to promote the growth of certain species of algae under certain conditions and thus in this way to eutrophication contribute to the waters. Albeit a clear clarification of the proportion of detergents and cleaning agents containing phosphates in the Water eutrophication not yet at the moment is possible, it still seems worthwhile to find potential nitrogen- and phosphorus-free substitutes for the previously in To develop detergent formulations used builder substances.

It is already known that nitrogen- and phosphorus-free builders are used to be used in detergent formulations. As such, starch derivatives such as dicarboxyl and carboxymethyl starch or polymeric carboxylic acids such as polymaleic acid and polyitaconic acid, as well as their copolymers with unsaturated carboxylic acids, olefins or short-chain unsaturated ones aliphatic ethers or alcohols are used. Farther Oxydiacetic acid, oxydisuccinic acid, cyclocarboxylic acid, such as benzene penta- or tetracarboxylic acid, were used as structural substances, Esters of polyethylene glycol and adipic acid, maleic acid, which contains sulfonate groups, and esters of / ethylene glycol and Tri- or tetracarboxylic acids proposed. After all it is from German Offenlegungsschrift 2,136,672 and 2,161,727 and from the publication by P. Berth, G. Jakobi and E. Schmadel in Chemiker-Zeitung 95. (1971), pages 548-553. known, poly-oo-hydroxiacrylic acid or polyacrylic acid or their Alkali salts as builders for detergents and cleaning agents use.

The aforementioned substances have not proven to be structural substances that are satisfactory in every respect, since they are

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Substances not sufficiently explained at the beginning Have builder properties and are therefore not satisfactory Result in washing results. In addition, there is also a lack of economical processes for the production of these in some cases Links. The aforementioned disadvantages of the known builders are not inherent in the builders of the invention.

It has now been found, surprisingly, that a copolymer of α-hydroxiacrylic acid and acrylic acid, or. the corresponding Sodium salt, has a much better ability to sequester polyvalent metal ions than, for example Poly-ot-hydroxiacrylic acid or polyacrylic acid or their alkali or Ammonium salts.

The invention thus relates to builders for detergents and cleaning agents, which are characterized in that they consist of copolymers of α-hydroxy acrylic acid and acrylic acid with an acrylic acid content of about 9 to 85 mol% and a relative viscosity of 1 percent by weight solutions of the copolymers in aqueous 2 normal sodium hydroxide solution at 20 ⁰ C from about 0.05 to about 1.0.

The lime-carrying capacity of the copolymer according to the invention is considerably above the amount to be expected stoichiometrically, i.e. that the copolymer gives an unexpected synergistic effect. This result is all the more astonishing than according to P.Berth, G. Jakobi and E. Schmadel, Chemiker-Zeitung 9J? (1971), pp. 548-553, it is known that the lime-carrying capacity of polyacrylic acid is pretty much that corresponds to the stoichiometric ratio. Due to the partial use of cheap acrylic acid for the production of the copolymer are its production costs compared to poly-oc-hydroxiacrylic acid significantly reduced. The products according to the invention are therefore suitable for use as a structural substance in detergents and detergents Detergents.

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A preferred feature of the builders according to the invention is that the acrylic acid content 16 to 50 Mo 1% and the relative viscosity of 1 gev. One percent solutions of the copolymers in aqueous 2 normal sodium hydroxide solution at 20 ° C. are about 0.1 to 0.8.

It has proven particularly advantageous to use the water-soluble ones Salts such as the alkali or ammonium salts of the copolymers of α-hydroxy acrylic acid and acrylic acid as Use detergent and cleaning agent components. The invention Builders' can be used in an amount of about 10 to 90 weight? 6, especially 20 to 60 weight ^ in Detergents and cleaning agents.

Another object of the invention are detergents and cleaning agents based on anionic, cationic, zwitterionic, ampholytic and / or nonionic surfactants and optionally other additives, which are characterized in that they are copolymers of α-hydroxy acrylic acid and acrylic acid with an acrylic acid content of about 9 to 85 Mo1% and a relative viscosity of 1 percent by weight solutions of the copolymers in aqueous 2N sodium hydroxide solution at 20 ⁰ C of about 0.05 to about 1.0 included.

The proportion of acrylic acid in the copolymers is preferably 16 to 50 mol% and the relative viscosity of the 1st weight percent solutions of the copolymers in aqueous 2 normal sodium hydroxide solution at 20 ° C about 0.1 to 0.8.

In the detergents and cleaning agents according to the invention preferably the water-soluble salts, such as the alkali or ammonium salts of the copolymers. The copolymer content in the detergent and cleaning agent can be about 10 to 90 weight ^, in particular about 20 to 60 weight ^.

AO98S1 / 0940

In addition to the builders according to the invention, conventional builders, such as e.g. Alkali polyphosphates may be included. Anionic or nonionic substances are preferred as surfactant components in the detergent. ■

Among anionic surfactants are the water-soluble salts of higher fatty acids or resin acids, such as sodium or potassium soaps of hardened or unhardened coconut, palm kernel or rapeseed oil, as well as tallow and corresponding mixtures thereof to understand. Furthermore, among anion-active substances for the purposes of the invention are higher alkyl-substituted, mononuclear, aromatic sulfonates, such as alkylbenzenesulfonates with 9 to 14 carbon atoms in the alkyl radical, alkyltoluene sulfonates, "alkylxylene sulfonates, Alkylphenolsulfonate or Alkylnaphthalinsulfonate as well as sulfated aliphatic alcohols or alcohol ethers such as sodium or potassium lauryl or hexadecyl sulfate, triethanolamine lauryl sulfate, Sodium or potassium oleyl sulfate, as well as the sodium or potassium salts of about 2 to 6 moles Ethylene oxide ethoxylated lauryl sulfate and the like to understand.

Used as non-ionic surfactants for detergents and cleaning agents generally denotes compounds which have an organic hydrophobic group and a hydrophilic residue. Examples for such nonionic surfactants are the condensation products of alkylphenols with ethylene oxide or of higher Fatty alcohols with ethylene oxide, as well as the condensation products of polypropylene glycol with ethylene oxide or propylene oxide as well the condensation products of ethylene oxide with the reaction product of ethylene diamine and propylene oxide. Long chain too tertiary amine oxides belong to the group of compounds mentioned above.

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Finally, in the series are those according to the invention as a surfactant component The following products with ampholytic or zwitterionic character are suitable for washing and cleaning agents Incorporate compounds: derivatives of aliphatic, secondary and tertiary amines or quaternary ammonium compounds with 8 to 18 carbon atoms and a hydrophilic group in the aliphatic Remainder, such as sodium 3-dodecylaminopropionate, sodium 3-dodecylaminopropanesulfonate, 3- (N, N-dimethyl-N-hexadecylamino) propane ^ 1-sulfonate or fatty acid amidoalkyl-N, N-di [nethylacetobetaine, where the fatty acid has 8 to 18 carbon atoms and the alkyl radical 3 carbon atoms contains.

Other additives that are also part of the invention Washing and cleaning agents can be, for example, the alkali or ammonium salts of sulfuric acid, silicic acid , Carbonic acid, boric acid, alkylene, hydroxy alkylene, or Aminoalkylenephosphonic acid, as well as bleaching agents, stabilizers for peroxide compounds and water-soluble organic complexing agents. Specifically, the last-mentioned groups of compounds include sodium perborate mono- or tetrahydrate, alkali metal salts Peroximono- or disulfuric acid, peroxohydrates of ortho-, Pyro- and polyphosphates, water-insoluble precipitated magnesium silicate, as well as the alkali salts of iminodiacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid.

Substances that increase the dirt-carrying capacity of washing liquors, such as carboxymethyl cellulose, polyvinyl alcohol, polyvinyl pyrolidone or are suitable as foam regulators, such as mono- and dialkyl phosphoric acid esters with 16-20 carbon atoms in the alkyl radical, as well as whiteners, disinfectants and / or proteolytic enzymes be additional components of the detergent and cleaning agent.

The builders according to the invention or those containing them Detergents and cleaning agents are considered technically advanced

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to be designated because they prevent or delay the precipitation of calcium ions in the washing liquor to a considerable extent and also form stable dispersions with both hydrophilic and hydrophobic dirt particles. Another benefit is to see in it that these structural substances contain no phosphorus or nitrogen and they thus the eutrophication of the do not favor natural waters. The lime-bearing capacity of the copolymers in the detergents and cleaning agents according to the invention surprisingly exceeds that by more than that Double the stoichiometrically calculable value, while in the case of polyacrylic acid or its sodium salt the value of stoichiometrically calculable lime carrying capacity almost coincides with the actual value. Somewhat more favorable conditions than in the case of polyacrylic acid are in the case of polyoxyhydroxiacrylic acid before, but there is also a striking difference compared to the builder according to the invention.

The invention is to be explained in more detail by the following examples, examples 1-6 showing the preparation of the builders according to the invention, while Examples 7 and 8 describe the effectiveness of the builders with regard to the lime carrying capacity or in the washing test is explained in the presence of other detergent components.

example 1

A mixture of 213 g (2 mol) of o-chloroacrylic acid and 1.5 liters of benzene was ^{heated to 80 °} C. in a polymerization vessel, and 1 g of benzoyl peroxide was added to the mixture. 72 g (1 mol) of acrylic acid were then added dropwise to the mixture in the course of 30 minutes with vigorous stirring. After adding

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of a further 2 g of benzoyl peroxide, the mixture was ^{left at 80 0} g for a further 5 hours, then cooled, and the polymer was filtered off and dried. 286 g of copolymerizate with a chlorine content of 24.1 % were obtained. Taking into account the fact that traces of HCl gas were released during the polymerization, the acrylic acid content of the copolymer was 34 mol%. The relative viscosity of a 1 percent by weight solution of the polymer in dimethylformamide at 25 ° C. was 0.63.

For the production of a copolymer from α-hydroxiacrylic acid and acrylic acid, 80 g of the above-described chlorine-containing copolymer were stirred into 800 ml of boiling water and incorporated constant vigorous stirring for 3 hours. The accruing finely powdered hydrolyzate was filtered off and dried. The yield was 55 g.

A 1 weight percent solution of the polymer in aqueous two normal NaOH had a relative viscosity of 0.34 at 20 ⁰ C. . ".- ■■ .. ■

Example 2

It was a mixture of 213 g (2 mol) α-chloro acrylic acid, 144 g (0.2 mol) of acrylic acid and 2 1 Essovarsol ^ (mineral oil fraction from Esso with the boiling range 144-175 ⁰ C) in a polymerization vessel at 80 ⁰ C heated and then treated with 2.13 g of benzoyl peroxide. The mixture was ^{stirred at 80 °} C. for 5 hours and afterwards. The polymer is filtered off when it cools. The polymer was washed with low-boiling petroleum ether and dried. 222 g of polymer with a chlorine content of 28.6 % and an acrylic acid content of 9 mol% were obtained.

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140 g of the above-described polymer were boiling in 1.5 l Stir in water and, as in Example 1, in an α-hydroxiacrylic acid Polymer transferred. The yield was 86 g. The relative viscosity of a 1 percent by weight The solution of the polymer in two normal NaOH was 0.15 at 20.degree.

Examples 3 - 5

The procedure was analogous to Example 2, but only the amount of acrylic acid used and the amount of starter were varied. The test results obtained are in Table 1 summarized.

Table 1

example 3 4th ■ 5 A. 28.8 72.0 144.6 B. 2.13 3.0 3.6 C. 236.0 280.0 353.0 D. 26.7 22.5 18.3 E. 17.0 34.0 50.0 F. 0.57 0.48 0.52 G 89.0 97.0 104.0 H 0.20 0.30 0.36

A = amount of acrylic acid used (g)

B = amount of benzoyl peroxide used (g) C = yield of chlorine-containing copolymer (g) D = chlorine content of the copolymer (%) E = proportion of acrylic acid in the chlorine-containing polymer (mol%)

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F = relative viscosity of a 1 percent by weight solution of the

chlorine-containing polymer in dimethylformamide at 25 ° C G = yield of hydrolyzed copolymer (^) H = relative viscosity of a 1 percent by weight solution of the hydrolyzed polymer; in aqueous two-normal NaOH at 20 ° C.

Example 6

213 g (2 mol) of .alpha.-chloro acrylic acid were dissolved in a polymerization vessel in 7.5 1 'Essovarsol ^ and heated to 80 ⁰ C. After adding 3.5 g of benzoyl peroxide, 720 g (10 mol) of acrylic acid were added dropwise over the course of 5 hours with vigorous stirring the polymer was filtered off, washed with low-boiling petroleum ether and dried. 938 g of polymer with a chlorine content of 7.5 % were obtained. The proportion of acrylic acid was 84 mol%. The viscosity of a 1% solution of the copolymer in dimethylformamide at 25 ° C was 0.79.

80 g of the copolymer in 1 l of water were used for the hydrolysis Cooked for 3 hours. The solution was then evaporated to dryness. The yield of hydrolyzate was 69 g. · Die The viscosity of a 1 percent by weight solution of the polymer in 2η aqueous NaOH at 20 ° C. was 0.55

Example 7

The lime-carrying capacity (KTV) was that of the examples 1-6 produced hydrolysis products by titration of a aqueous solution containing sodium carbonate containing 0.2% by weight of the hydrolysis product and at a pH of

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10 was adjusted with an aqueous 0.05 normal calcium acetate solution determined until permanent cloudiness occurs. The measure for the lime-bearing capacity expresses how many milligrams of calcium ions are kept in solution by 1 g of the hydrolysis product.

The stoichiometric lime load capacity of the hydrolysis products can be calculated using the following formula:

Atomic weight approx. 20,000

KTV = x 1000 =

2 χ Ä Ä

mg g

where Ä means the equivalent weight of the hydrolysis product. The latter was determined by acidimetric titration.

In Table 2 below, the values obtained for the lime-bearing capacity of the products according to the invention are compared to the corresponding values of the polyacrylic acid or polyoxyhydroxiacrylic acid set.

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Tabel

81.4 Lime-bearing capacity effectively product 82.9 theoretically 310 According to example 1 82.8 246 .. 409 H ti 2. 81.5 241 425 Il If / J 84.5 242 464 11 H 4 74.7 245 684 ir 11 5 72.3 237 507 11 11 5 82.5 ■ 268 274 Poly-acrylic acid 277 265 Poly-oc-hydroxy 242 acrylic acid

Table 2 shows the superiority of the products according to the invention over the comparison products with regard to the lime-bearing capacity, in that the first-mentioned products keep far more Ca ⁺⁺ ions in solution than the comparison substances.

The polyoxyhydroxiacrylic acid shown in Table 2 as a comparative product was made as follows:

a) In a round-bottom flask equipped with a stirrer and reflux condenser, a mixture of 100 g of oc-chloroacrylic acid, 400 ml of benzene and 1 g of benzoyl peroxide was heated to boiling for 3 hours under a nitrogen atmosphere. The precipitated polymer was separated off and ^{dried at 40 °} C. in a vacuum. The yield of poly-oc-chloroacrylic acid was 100% of theory.

b) A saturated at 30 ⁰ C, aqueous solution of PoIya-chloracry! prepared acid and this solution is heated for 2 hours to boiling. The precipitated hydrolyzate "was chloride-

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washed free and dried at 60 ° C in vacuo. The yield of poly-oc-hydroxy-acrylic acid was 77 g or 100% of theory. The hydrolyzate had a molecular weight of 2800 and a lime binding capacity of 265 mg Ca / g.

c) By neutralizing 25 g of the poly-oc-hydroxiacrylic acid with 25 g of a 50% sodium hydroxide solution and evaporation of the water the sodium salt was obtained.

Example 8

The detergency of washing liquors was determined on the basis of washing tests with a constant concentration of known detergent components, but different amounts of inventive Builder A or B or C was determined and the results obtained are shown in FIG. Among builders A, B and C are the sodium salts of those according to Examples 1, 3 and 6 hydrolysis products produced. For comparison, analogous washing tests were carried out using the known ones Builders D and E carried out and the values obtained in this way for the detergency also in Figure 1 in the form of Curves shown. Builder D is to be understood as meaning the sodium salt of a polyacrylic acid, its 40 percent by weight aqueous solution has a viscosity of 1900 centipoise at 25 ° C. Builder E relates to the sodium salt of polyhydroxiacrylic acid, the preparation of which has been described above.

The washing tests were carried out with a standard cotton fabric with Krefeld soiling in a launder-0 meter at a washing flute temperature carried out at 95 ° C. Standard fabrics with soiling from Krefeld are described in Kurt Lindner's book "Tenside, Textile auxiliaries - washing raw materials ", Wissenschafti. Verlagsgesellschaft Stuttgart (1964), Volume II, page 1837, defined,

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409 8-51 / 0940

The washing water had 20 German degrees of hardness and a pH value of 10. The washing time was 30 minutes and the liquor ratio, characterized by the ratio of (kg) laundry to (liter) washing liquor, 1:50 in the presence of 10 Steel balls.

After the prescribed washing time, the standard cotton fabric became Rinsed once hot and once cold with water of the same hardness and then in the remission photometer Elrepho from Zeiss measured the degree of whiteness using the R 53 filter. The detergency was determined by the difference method determined "which results from the following equation:

WK = % WG - %

where % WK = % detergency

% WG _x =% whiteness of the fabric gewaschenen- ^L

% WG _h =% whiteness of the unwashed fabric.

A wash liquor with the following composition was used to carry out the washing tests:

0.45 g / l dodecylbenzenesulfonate

0.15 g / l ethoxylated tallow fatty alcohol with 11 moles of ethylene oxide per; Moles of alcohol

0.15 g / l hardened tallow soap 0.15 s / l magnesium silicate 0.15 g / l sodium silicate 1.25 g / l sodium perborate tetrahydrate 0.15 g / l sodium sulfate 0.05 g / l Tylose ^:

0.2-2 g / l builder A, B, C, D or E

ad 1000 ml of water.

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The washing power achieved with the individual wash liquors is demonstrated by the curves of curves A to E, curves A, B and C showing the results of washing tests with the builders A, B and C according to the invention and curves D and E showing the results of washing tests represent known builders D and E. It can be seen from this that, for example, with an amount of builder of 1.8 g / l wash liquor with the builders A, B and C, a washing power of 35.5%, 34.6 % and 34.4 % is achieved, while among the Under the same conditions, builders D and E only give a washing power of 32.6 % and 33.0 % , respectively. These results also show the technical superiority of the builders according to the invention over the known builders in the standard washing test.

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Claims (12)

Patent claims: 1. Builders for detergents and cleaning agents, characterized in that they consist of copolymers of oc-hydroxy-acrylic acid and acrylic acid with an acrylic acid content of about 9 to 85 mol% and a relative viscosity of the 1 percent by weight solutions. Copolymers in aqueous 2 normal sodium hydroxide solution at 20 ⁰ C from about 0.05 to about 1.0 exist. 2. Builders according to claim 1, characterized in that the acrylic acid content 16 to 50 Mo1% and the relative viscosity of the 1 percent by weight solutions of the copolymers in aqueous 2 normal: be about 0.1 to 0.8. Sate in aqueous 2 normal sodium hydroxide solution at 20 ° C 3. Builders according to claim 1 or 2, characterized in that the water-soluble salts of the copolymers of cx-hydroxiacrylic acid and acrylic acid are used as washing and cleaning agents. 4. Builders according to Claim 3, characterized in that the alkali or ammonium salts of the copolymers of oc-hydroxiacrylic acid and acrylic acid are used as washing and cleaning agents. ■ 5. Builders according to claims 1-4, characterized in that they are contained in detergents and cleaning agents in an amount of about 10 to 90 weight ^. 6. Builders according to claim 5, characterized in that they are used in detergents and cleaning agents, preferably in one • Amounts of around 20 to 60 % by weight are included. - 18 - - 409851/0940 7 Detergents and cleaning agents based on anion-active, cationic, zwitterionic, ampholytic and / or non-ionic surfactants and possibly other additives, / »characterized by a content of C © polymers of α-hydroxy acrylic acid and acrylic acid with an acrylic acid content of about 9" to 85 Mo 1% and a relative viscosity of the '! Weight percent solutions of the copolymers in aqueous 2 normal
about 0.05 to about 1.0. in aqueous 2 normal sodium hydroxide solution at 20 ° C of 8. Washing and cleaning agent according to claim 7, characterized in that the acrylic acid content in the copolymers 16 to 50 mol% and the relative viscosity of the 1 percent by weight solutions of the copolymers in aqueous 2 normal sodium hydroxide solution at 20 ⁰ C about 0.1 to 0, 8. 9. Washing and cleaning agents according to claim 7 or 8, characterized in that they contain the water-soluble salts of the copolymers as builder substances. 10. Washing and cleaning agents according to claim 9 » characterized in that they contain the alkali or ammonium salts of the copolymers as builders. 11. Washing and cleaning agents according to claim 7-10, characterized in that they have a copolymer content of about 10 to 90% by weight. 12. Washing and cleaning agents according to claim 11, characterized in that they have a copolymer content of preferably about 20 to 60 weight ^. 409851/0940