JPH0726116B2 - Detergent composition containing odor-purifying protease and perfume - Google Patents

Description

TECHNICAL FIELD The present invention relates to an odor-purifying proteolytic enzyme (protease).
And a detergent composition containing a predetermined fragrance. The composition is preferably a heavy duty liquid detergent, but can be any household product that incorporates both proteases and perfumes, such as hand creams, lotions, solid soaps, liquid soaps, granular detergents, and light detergents. It is a duty liquid detergent.

A significant drawback of using enzymes in household products is the unpleasant odor contribution of traditional quality enzyme stock. These enzyme stocks are a complex mixture obtained from fermentation processes. They usually contain significant amounts of offensive odor contaminants and colorants. Proteases have a particularly strong and unpleasant odor. This drawback has traditionally been addressed by limiting the amount of enzyme used in the product or masking the enzymatic odor with perfume oil. The limiting enzyme amount limits the efficacy of the product. Fragrance masking is not fully effective and is limited by cost and product aesthetics.

The present invention uses a highly purified odor-purifying protease stock as well as certain fragrances to reduce or eliminate malodorous proteases. This gives the formulator greater flexibility in choosing the optimal amount of enzyme.

Background Art U.S. Pat.No. 4,318,818 discloses a heavy duty liquid detergent containing an enzyme, preferably a protease, and an enzyme stabilizing system consisting of calcium ions and a low molecular weight carboxylic acid or salt, preferably formate. is doing. The composition may contain various surfactants and optionally detergent ingredients, such as fragrances.

U.S. Patent Application No. 537,321, filed September 29, 1983, discloses a light duty liquid detergent containing a protease and a mild detergent surfactant.

SUMMARY OF THE INVENTION The present invention provides (a) from about 0.005 to about 0.1 Anson units (An) per gram of composition.
a proteolytic enzyme selected from the group of alcalase and maxatase, which has a detectable odor at a concentration of less than about 0.002 Anson units per gram of distilled water. No), and (b) phenylethyl alcohol, linalool, geraniol, citronellol, cinnamic alcohol, isobornyl acetate, benzyl acetate, p-tert-butylcyclohexyl acetate, linalyl acetate, dihydro-nor-dicyclopentadienyl acetate, Dihydro-nor-dicyclopentadienyl propionate, amyl salicylate, benzyl salicylate, p-isopropyl α-octylhydrocinnamaldehyde, hexylcinnamaldehyde, hydroxycitronellal, heliotropin, anisaldehyde, citral, dextrolyl Nene, coumarin, ionone γ-
Methyl, methyl β-naphthyl ketone, γ-undecalactone, eugenol, muskoxylol, 1,3,4,6,7,8
-Hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-γ-2-benzopyran, 4-acetyl-6-tert
-Butyl-1,1-dimethylindane, 6-acetyl-1,
1,3,4,4,6-hexamethyltetrahydronaphthalene, β
-Naphthylethyl ether, methyl eugenol, methyl cedrenyl ketone, patch lily, lavandin, geranyl nitrile, α-ionone, β-ionone, α-ionone and β
-A mixture of yonones, benzylisoeugenol, amylcinnamic aldehyde, β, γ-hexenol, orange C
P, o-tert-butylcyclohexyl acetate, 2-methyl-3- (p-isopropylphenyl) propionaldehyde, trichloromethylphenylcarbinyl acetate, nonanediol-1,3-acetate, methyldihydrodiasmonate, iso Perfume from about 0.001 to about 2 selected from the group consisting of phenoxyethyl butyrate, citronella, citronellal, citratar, tetrahydromuguol, ethylene brushlate, musk ketone, muscutibetin, phenylethyl acetate, oak moss 25%, hexyl salicylate, eucalyptol, and mixtures thereof. It relates to a detergent composition, characterized in that it consists of weight%.

Proteolytic enzyme The composition of the present invention has a composition of about 0.005 to about 0.1, preferably about 0.01 to about 0.07, and most preferably about 0.012 to about 0.01 per gram of the composition.
It contains a sufficient amount of proteolytic enzyme to give 0.04 Anson units of activity. In the present invention, two commercial enzyme preparations are used as proteolytic enzymes, namely "Alcala" sold by Industries, Novo, Copenhagen, Denmark.
se) ”and the Gist of Delft, the Netherlands-Brocades (Gi
st-Brocades) and is used by selecting from the group consisting of "Maxatase".

The protease in the present invention is about 0.02 per 1 g of distilled water.
It is purified prior to incorporation into the final composition so that it has no detectable odor at concentrations below Anson units. They preferably have no detectable odor at concentrations of less than about 0.0025, more preferably less than about 0.003 Anson units per gram of distilled water. As used herein, "threshold odor detection concentration" refers to the concentration at which a panel of at least three professional grades will first detect a protease odor by moving from a highly diluted to a low diluted solution of a protease formulation in distilled water. It is calculated by averaging.

The protease of the present invention may be odor purified by any method known in the art. Examples include Bauer,
Israel J. Chem. 5 (3) pp. 117-120 (1967) "Enzyme precipitation and their stability at high alcohol concentrations".
And Sugiura et al., Pharmacy, 1967, Vol.27 (2), No. 13
The solvent precipitation method described on page 5 to page 139 "Enzyme preparation".

Solvent-initiated precipitation of a commercial crude enzyme solution causes most of the enzyme activity to precipitate from solution, and most of the odor and color impurities remain in the supernatant. Decantation or centrifugation of the supernatant from the precipitated enzyme yields an enzyme fraction with abundant enzyme activity / g and improved odor and color.

Various solvents or combinations of solvent pairs can be used to produce the desired precipitation. For example, methanol, ethanol, acetone, other organic solvents, and combinations of organic solvents, and combinations of organic solvents with water can be used. Highly preferred solvents are water and ethanol 30
~ 70% by weight in combination. This seems optimal for maximal recovery of activity and prevention of enzyme inactivation.

The purified enzymes of the invention also provide benefits in the area of product color stability.

Fragrance composition is phenylethyl alcohol, linalool,
Geraniol, citnerol, cinnamic alcohol, isobornyl acetate, benzyl acetate, p-tert-butylcyclohexyl acetate, linalyl acetate, dihydro-nor-dicyclopentadienyl acetate, dihydro-nor-propionate.
Dicyclopentadienyl, amyl salicylate, benzyl salicylate, p-isopropyl α-octylhydrocinnamic aldehyde, hexyl cinnamic aldehyde, hydroxycitronellal, heliotropin, anisaldehyde,
Citral, dextrolimonene, coumarin, yonon gamma
-Methyl, methyl β-naphthyl ketone, γ-undecalactone, eugenol, muskoxylol, 1,3,4,6,7,
8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-γ-2-benzopyran, 4-acetyl-6-tert
-Butyl-1,1-dimethylindane, 6-acetyl-1,
1,3,4,4,6-hexamethyltetrahydronaphthalene, β
-Naphthylethyl ether, methyleugenol, methylcedrenyl ketone, patchouli, lavandin, geranylnitrile, α-ionone, α, β-ionone, benzylisoeugenol, amyl cinnamic aldehyde, β, γ-hexenol, orange CP, acetic acid o -Tert-butylcyclohexyl, 2-methyl-3- (p-isopropylphenyl) propionaldehyde, trichloromethylphenylcarbinyl acetate, nonanediol-1,3-acetate,
Selected from the group consisting of methyl dihydrodiyasmonate, phenoxyethyl isobutyrate, citronella, citronellal, citratar, tetrahydromugol, ethylene brushlate, musk ketone, musktibetin, phenylethyl acetate, oak moss 25%, hexyl salicylate, eucalyptol, and mixtures thereof. Fragrance about 0.
001 to about 2% by weight, preferably about 0.01 to about 1% by weight, more preferably about 0.2 to about 0.5% by weight.

These perfume materials are commercially available and are well known to perfume formulators in the wash area. Their combined use with odor-purifying proteases can significantly improve the odor of household products containing enzymes. Alternatively, a product with comparable odor properties is obtained using higher amounts of enzyme.

Preferred perfume materials are those that provide maximum odor improvement within the final product composition containing the purified proteases of the present invention. These fragrances include, for example, phenylethyl alcohol, linalool, geraniol, cinnabar alcohol,
Isobornyl acetate, benzyl acetate, p-tert-butylcyclohexyl acetate, linalyl acetate, dihydro-nor-dicyclopentadienyl acetate, dihydro-nor-dicyclopentadienyl propionate, amyl salicylate, p-
Isopropyl α-octylhydrocinnamaldehyde, hexyl cinnamaldehyde, hydroxycitronellal,
Heliotropin, citral, dextrolimonene, yonone γ-methyl, methyl β-naphthyl ketone, γ-undecalactone, eugenol, muskoxylol, 1,3,
4,6,7,8-Hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-γ-2-benzopyran, 4-acetyl-6
-Tert-butyl-1,1-dimethylindane, 6-acetyl-1,1,3,4,4,6-hexamethyltetrahydronaphthalene, β-naphthylethyl ether, methyl eugenol, methyl cedrenyl ketone, patch lily, Lavandin, geranyl nitrile, α-ionone, benzylisoeugenol, amyl cinnamic aldehyde, β, γ-hexenol, o-tert-butylcyclohexyl acetate, trichloromethylphenylcarbinyl acetate, nonanediol-1,
3-acetate, methyl dihydrodiasmonate, citral, ethylene brassielate, 25% oak moss, and mixtures thereof.

Particularly preferred of said group are phenylethyl alcohol, linalool, geraniol, isobornyl acetate,
Benzyl acetate, p-tert-butylcyclohexyl acetate,
Linalyl acetate, amyl salicylate, hexyl cinnamic aldehyde, hydroxycitronellal, methyl β-naphthyl ketone, eugenol, muskoxylol, 6-acetyl-1,1,3,4,4,6-hexamethyltetrahydronaphthalene, geranylnitrile, Ethylene brushes, and mixtures thereof.

Optionally Formulated Ingredients The detergent compositions of the present invention can include any ingredient known to be used in such compositions. For example, they may include from about 1 to about 75% by weight of detergent surfactant, preferably about 10%.
To about 50% by weight, more preferably about 15 to about 40% by weight. Surfactants include various nonionic surfactants, anionic surfactants, cationic surfactants, zwitterionic surfactants, and amphoteric surfactants such as U.S. Pat. No. 4,318,81.
It may be selected from those described in No. 8.

Preferred anionic surfactants are, C ₁₀ -C ₁₈ (preferably C ₁₂ -C ₁₆₎ alkyl sulphates, C ₉ -C ₁₅ with alkyl sulphates per mole average 0 to about 4 ethylene oxide units (preferably the C ₁₁ -C ₁₃₎ alkylbenzene sulfonates, C ₁₂ -C ₁₈ paraffin sulfonates,
It is a C ₁₂ -C ₁₈ esters of alkyl glyceryl ether sulfonate and α- sulfonated C ₁₂ -C ₁₈ fatty acids.

Preferred nonionic surfactants are of the formula R ¹ (OC ₂ H ₄ ) nOH, where R ¹ is a C ₁₀ -C ₁₆ alkyl group or a C ₈ -C ₁₂ alkylphenyl group and n is about 3 to. Is about 9) ethoxylated alcohol [wherein the nonionic surfactant is HLB
(Hydrophilic / lipophilic balance) of about 10 to about 13]. C ₁₂
~ C ₁₅ alcohol and about 3 to about 7 per mole of alcohol
Condensates of moles of ethylene oxide, for example an alcohol per mole to about 6.5 moles of C ₁₂ -C ₁₃ alcohols engaged ethylene oxide condensed is particularly preferred.

The preferred liquid detergents of the present invention also contain an enzyme stabilization system. This enzyme stabilization system is preferably the above-mentioned US Pat.
It is a mixture of short chain carboxylates and calcium ions as described in 318,818.

The short chain carboxylates are preferably water-soluble, most preferably formates such as sodium formate. Short chain carboxylates are about 0.25% to about 10%, preferably about 0.3%.
To about 3%, more preferably about 0.5% to about 2.0%. At higher product pH (8.5-10), only formate is suitable.

Any water soluble calcium salt, such as calcium acetate, calcium formate and calcium propionate,
It can be used as a source of calcium ions. The composition should contain from about 0.01 to about 30 millimoles / calcium ion, preferably from about 0.1 to about 15 millimoles / calcium ion. When there are substances that complex calcium ions, such as detergent builders, it is necessary to use large amounts of calcium ions so that there is always some minimum amount available for the enzyme. However,
Excellent enzyme stability is achieved using very low amounts of calcium ions, when formate is used at particularly low pH (less than about 8.5).

The pH of the preferred heavy duty liquid detergent of the present invention is
It is about 6.5 to about 10, preferably about 7 to about 8.5. Suitable pH
Buffering agents are, for example, mono-, di- and triethanolamine. Triethanolamine is the preferred buffer when the product pH is about 8.5 to about 10. When soap or fatty acids are present, the preferred pH is about 7
~ About 8.5.

Also, preferred heavy duty liquid detergents include other enzymes, particularly amylases such as "Rapidase" sold by Gist Brokers and "Termamyl sold by Novo Industries. ) ”Can be included. Purifying amylase using the above-described protease purification methods can also impart odor and / or color benefits to certain end products. However, since amylase is inherently less odorous and is typically used in much lower amounts than proteases, the malodor is generally not severe.

A preferred light duty dishwashing liquid composition of the present invention is described in US patent application Ser. No. 537,32 filed Sep. 29, 1983.
No. 1 specification. The present invention is described in U.S. Pat.
It may also be used in the dishwashing liquid detergents described in 33,779 and US Pat. No. 4,316,824.

The present invention is also useful in skin conditioning compositions such as those described in US Pat. No. 4,370,319.

The following example illustrates the composition of the present invention. All parts, percentages and ratios used herein are by weight unless otherwise noted.

Example I Commercially available odor purified protease solutions are 1%, 0.5%, 0.25%, 0.125%, 0.0625% and 0.
It was diluted to a concentration of 03125%. The solution was compared with distilled water starting with a 0.03125% solution and transferred to a more concentrated solution to determine the threshold odor detection concentration (TODC) by a panel of professional graders. The results are as follows.

These results indicate that purified commercial grade protease solutions, especially maxatase, provide a significant reduction in enzymatic odor. An improvement in enzyme color was also observed with purified protease.

In a similar comparison between the commercially available purification grade α-amylase, Termamyl (activity 305-326 KNu / g), no odor reduction was observed, but an improvement in color was observed.

TODC 0.03125% was determined to produce an unacceptable enzymatic odor and TODC 0.0625% was determined to produce a borderline acceptable enzymatic odor when the protease solution was added to the following heavy duty liquid detergents: And TODC 0.1
25% was determined to produce an acceptable enzymatic odor.

Composition A Ingredient wt% C _{12 to 14} alkyl ethoxylate 9.4 (1) Sodium sulfate (acid basis) (8.8) C _{12 to 13} alkyl polyethoxy les 21.5 over preparative (6.5) Ethanol 5.7 diethylenetriaminepentaacetic acid 0.2 Sodium Makisataze 0.026 Anson units / g Tamuamiru 0.51 KNU / g sodium formate 1.6 calcium formate 0.1 water and minor components balance pH 7.5 composition B ingredient wt% C _{14 to 15} alkyl polyethoxylate 18.0 rate (7) ^* coconut tree alkyl dimethyl amine oxide 1.0
Ditallow dimethyl ammonium chloride ^** 3.0
TEPA-E _15-18 ^*** 1.5 Ethanol 7.5 Maxatase 0.015 Anson Unit / g Tamamyl 0.51 KNu / g Sodium Formate 1.2 Calcium Hydrochloride 0.025 Water and Trace Components Residual pH 7.0 * Alcohol and monoethoxylated alcohol are removed * * 60-65% Unsaturated Tallow *** Tetraethylenepentaimine ethoxylated with 15-18 mol (average) ethylene oxide at each hydrogen position Example II Threshold odor detection 0.03125% commercially available maxater Zestsk solution or threshold odor detection concentration
Odor-purified maxatase solutions with 0.125 (each having an initial activity of 2.0 Anson units / g) per gram of composition
Example I in an amount sufficient to give 0.026 Anson units of activity
Was added to a sample of Composition A (excluding enzyme). Each sample was 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-γ-2-benzopyran (0.05%
0.1% by weight of the following perfumes.

Samples should be 5 or 6 using the scales 1-10 below.
Graded for odor by a panel of human graders.

The samples were graded again after 12 and 35 days. The results after grade averaging are as follows.

Here, "stock" refers to the case where the enzyme is not purified.

These results show that all combinations of purified maxatase as well as all test perfume substances except α-terpineol improve product odor.

Example III Commercially available maxatase stock solution with a threshold odor detection level of 0.03125% or a threshold odor detection level
Odor purified maxatase solutions with 0.09375% (each having an initial activity of about 2.0 Anson units / g) are
Composition C was added to a sample of composition C in an amount sufficient to provide 0.022 Anson units per activity. Each sample contained 0.1% by weight of the fragrance listed in Table II.

Composition C Ingredient wt% C _{12 to 14} alkyl ethoxylate 9.4 (1) Sodium sulfate (acid basis) (8.8) C _{12 to 13} alkyl polyethoxylate 21.5 (6.5) Ethanol 6.2 Sodium diethylenetriamine pentaacetic acid 0.2 TEPA-E _{15 ~ 18} ^* 1.5 Tamamyl 0.51KNu / g Sodium formate 1.6 Calcium formate 0.1 Water and trace components balance pH 7.5 * Tetraethylenepentaimine ethoxylated with 15-18 moles (average) of ethylene oxide at each hydrogen position. The results after grade averaging as described were:

Preferred perfume materials according to the invention are stored for 11 days, 12 days or 35 days.
Examples II and III that give the greatest improvement in odor after days.

Example IV The odor-purifying proteases of the invention and certain perfume substances are also preferably used in the following heavy duty liquid detergent compositions. Component Weight% C ₁₃ Linear alkylbenzene sulfonic acid 7.2 C _14-15 Alkyl polyethoxylate (2.25) Sulfuric acid 10.8 C _12-13 Alcohol polyethoxylate (6.5) ^* 6.5 C ₁₂ Alkyltrimethylammonium chloride 1.2 C _12-14 fatty acid 13.0 Oleic acid 2.0 Citric acid (anhydrous) 4.0 Diethylenetriaminepentaacetic acid 0.23 Protease enzyme (2.0Au / g) 0.75 Amylase enzyme (375Amu / g) 0.16 TEPA-E _15-18 ^** 1.5 Monoethanolamine 2.0 Sodium ion 1.66 Potassium ion 2.65 Propylene glycol 7.25 Ethanol 7.75 Formic acid 0.66 Calcium ion 0.03 Trace components and water balance pH 8.65 at 10% concentration in water at 68 ° F (20 ° C) * Alcohols and monoethoxylated alcohols are removed ** Each hydrogen position Ethylene oxide ethoxylated with 15-18 moles (average) of ethylene oxide at Traethylene Pentimine

 ─────────────────────────────────────────────────── --Continued from the front page (56) Reference JP-A-57-85900 (JP, A) JP-A-57-85898 (JP, A) JP-A-58-117295 (JP, A) JP-A-54- 143540 (JP, A) US Patent 379818 (US, A)

Claims (10)

[Claims] 1. A proteolytic enzyme selected from the group consisting of alcalase and maxatase in an amount sufficient to provide about 0.005 to about 0.1 anson units of activity per gram of composition (a) wherein the enzyme is 1 g of distilled water. Has no detectable odor at a concentration of less than about 0.002 Anson units per unit), and (b) phenylethyl alcohol, linalool, geraniol, citronellol, cinnamic alcohol, isobornyl acetate, benzyl acetate, p-tert-butyl acetate. Cyclohexyl, linalyl acetate, dihydro-nor-dicyclopentadienyl acetate, dihydro-nor-dicyclopentadienyl propionate, amyl salicylate, benzyl salicylate, p-isopropyl α-octylhydrocinnamaldehyde, hexyl cinnamaldehyde, hydroxy Citronellal, Helio Ropin, anise aldehyde, citral, dextroamphetamine limonene, coumarin, ionone γ-
Methyl, methyl β-naphthyl ketone, γ-undecalactone, eugenol, muskoxylol, 1,3,4,6,7,8
-Hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-γ-2-benzopyran, 4-acetyl-6-tert
-Butyl-1,1-dimethylindane, 6-acetyl-1,
1,3,4,4,6-hexamethyltetrahydronaphthalene, β
-Naphthylethyl ether, methyl eugenol, methyl cedrenyl ketone, patchouli, lavandin, geranyl nitrile, α-ionone, β-ionone, α-ionone and β
-A mixture of yonones, benzylisoeugenol, amylcinnamic aldehyde, β, γ-hexenol, orange C
P, acetic acid o-tert-butylcyclohexyl, 2-methyl-3- (p-isopropylphenyl) propionaldehyde, trichloromethylphenylcarbinyl acetate, nonanediol-1,3-acetate, methyldihydrodiamonate, isoacid acid Phenoxyethyl, citronella, citronellal, citratar, tetrahydromuguol,
A detergent composition characterized in that it comprises from about 0.001 to about 2% by weight of a perfume selected from the group consisting of ethylene brushlate, musk ketone, muscutibetin, phenylethyl acetate, 25% oak moss, hexyl salicylate, eucalyptol, and mixtures thereof. . 2. Proteolytic enzyme is about 0.
The detergent composition of claim 1 which provides an activity of from 01 to about 0.07 Anson units. 3. Proteolytic enzyme is about 0.
The detergent composition according to claim 1, which has no detectable odor at a concentration of less than Anson units. 4. Phenylethyl alcohol, linalool, geraniol, isobornyl acetate, benzyl acetate,
P-tert-butylcyclohexyl acetate, linalyl acetate,
Salicyl vinegar amyl, hexyl cinnamaldehyde, hydroxycitronellal, methyl β-naphthyl ketone, eugenol, muskoxylol, 6-acetyl-1,1,3,4,
A detergent composition according to claim 1 which contains a perfume selected from the group consisting of 4,6-hexamethyltetrahydronaphthalene, geranyl nitrile, ethylene brassilate, and mixtures thereof. 5. A detergent interface selected from the group consisting of (a) nonionic surfactants, anionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof. About 1 to about 75% by weight of the active agent, and (b) a proteolytic enzyme selected from the group consisting of alcalase and maxatase in an amount sufficient to provide about 0.005 to about 0.1 anson units of activity per gram of composition (the aforementioned enzymes. Has no detectable odor at concentrations less than about 0.002 Anson units per gram of distilled water), and (c) phenylethyl alcohol, linalool, geraniol, citronellol, cinnamic alcohol, isobornyl acetate, benzyl acetate, acetic acid. p-tert-butylcyclohexyl, linalyl acetate, dihydro-nor-dicyclopentadienyl acetate, dihydro-nor propionate -Dicyclopentadienyl, amyl salicylate, benzyl salicylate, p-isopropyl α-octylhydrocinnamic aldehyde, hexyl cinnamic aldehyde, hydroxycitronellal, heliotropin, anisaldehyde, citral, dextrolimonene, coumarin, ionone γ-
Methyl, methyl β-naphthyl ketone, γ-undecalactone, eugenol, muskoxylol, 1,3,4,6,7,8
-Hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-γ-2-benzopyran, 4-acetyl-6-tert
-Butyl-1,1-dimethylindane, 6-acetyl-1,
1,3,4,4,6-hexamethyltetrahydronaphthalene, β
-Naphthylethyl ether, methyl eugenol, methyl cedrenyl ketone, patchouli, lavandin, geranyl nitrile, α-ionone, β-ionone, α-ionone and β
-A mixture of yonones, benzylisoeugenol, amylcinnamic aldehyde, β, γ-hexenol, orange C
P, o-tert-butylcyclohexyl acetate, 2-methyl-3- (p-isopropylphenyl) propionaldehyde, trichloromethylphenylcarbinyl acetate, nonanediol-1,3-acetate, methyldihydrodiasmonate, phenoxy isobutyrate Ethyl, citronella, citronellal, citratar, tetradromgual,
A heavy tutee characterized in that it comprises from about 0.001 to about 2% by weight of a perfume selected from the group consisting of ethylene brassielate, musk ketone, muscutivetine, phenylethyl acetate, 25% oak moss, hexyl salicylate, eucalyptol, and mixtures thereof. Liquid detergent composition. 6. Proteolytic enzyme is about 0.01 per 1 g of the composition.
The composition of claim 5 which provides an activity of 2 to about 0.04 Anson units. 7. Proteolytic enzyme is about 0.
A composition according to claim 6 having no detectable odor at concentrations below 003 Anson units. 8. A composition according to claim 7 which contains from about 0.2 to about 0.5% by weight of perfume. 9. Phenylethyl alcohol, linalool, geraniol, cinnamic alcohol, isobornyl acetate, benzyl acetate, p-tert-butylcyclohexyl acetate, linalyl acetate, dihydro-nor-dicyclopentadienyl acetate, dihydropropionate-. Nor-dicyclopentadienyl, amine salicylate, p-isopropyl α
-Octylhydrocinnamaldehyde, hexylcinnamaldehyde, hydroxycitronellal, heliotropin, citral, dextrolimonene, yonone γ-methyl, methyl β-naphthyl ketone, γ-undecalactone, eugenome, muskoxylol, 1,3 , 4,6,7,8−
Hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-γ-2-benzopyran, 4-acetyl-6-tert-
Butyl-1,1-dimethylindane, 6-acetyl-1,1,
3,4,4,6-hexamethyltetrahydronaphthalene, β-
Naphthyl ethyl ether, methyl eugenol, methyl cedrenyl ketone, patchouli, lavandin, geranyl nitrile, α-ionone, benzylisoeugenol, amyl cinnamaldehyde, β, γ-hexenol, acetic acid o
Selected from the group consisting of -tert-butylcyclohexyl, trichloromethylphenylcarbinyl acetate, nonanediol-1,3-acetate, methyldihydrodiasmonate, citlatal, ethylene brushlate, oak moss 25%, and mixtures thereof. The composition according to claim 8, which contains a fragrance. 10. Phenylethyl alcohol, linalool, geraniol, isobornyl acetate, benzyl acetate,
P-tert-butylcyclohexyl acetate, linalyl acetate,
Amyl salicylate, hexyl cinnamic aldehyde, hydroxycitronellal, methyl β-naphthyl ketone, eugenol, muskoxylol, 6-acetyl-1,1,3,4,
10. A composition according to claim 9 containing a perfume selected from the group consisting of 4,6-hexamethyltetrahydronaphthalene, geranyl nitrile, ethylene brassilate, and mixtures thereof.