JPH0245599A - Liquid detergent containing enzyme - Google Patents

Abstract

PURPOSE: To provide a liquid detergent improved in enzyme sensibility and detergency to fatty stain, which contains a surface active agent, alkali protease enzyme, and enzyme stabilizer, and has specified physical property.

CONSTITUTION: An intended composition comprises (A) surface active agent, (B) alkali protease enzyme, and (C) polyol, boron compound, calcium ion, multifunctional amino compounds and an enzyme stabilizer selected from the above, wherein at 40.6°C, in the lapse of two weeks, 25% or more initial enzymic activity is shown, and at the time of dilution at the percentage of 0.2% in water detergent with liquid concentrate with pH of 0.5 or more, solution pH of 8.5 or more is attained, alkaline degree converted to Na₂O is 0.5%/g, and the moisture content is 5-80%.

COPYRIGHT: (C)1990,JPO

Description

[Detailed description of the invention] The present invention provides a liquid detergent containing enzymes including protease,
The invention relates to the use of such liquid detergents in washing processes, such as laundry processes, in particular to heavy duty liquid laundry detergents containing alkaline 10-tease enzymes (subtilisin type).

RuiΔ11 liquid laundry detergents are known and can provide cleaning, whitening, anti-resoiling and deodorizing performance comparable to known powder detergents, as well as ease of distribution, topical application for stain pre-treatment, and solubility. But it's convenient.

Liquid detergents present formulation challenges due to the need to maintain the stability of the ingredients in a homogeneous free-flowing form and the physical and chemical incompatibility of many of the desired ingredients.

It is common knowledge today to incorporate enzymes into laundry detergents. Many such detergents contain one or more proteolytic and/or Contains starch-degrading enzymes. The incorporation of enzymes into detergent powders has become commonplace because in powders enzymes do not come into close contact with surfactants and other chemicals that can degrade enzymes, cause them to lose enzyme activity and reduce efficacy. ing.

Despite significant improvements in enzyme stabilization systems, the incorporation of enzymes into liquid detergents remains a difficult problem.

Since product pH acts to destabilize most common proteolytic enzymes, enzyme stability problems are a function of system pH.
increases as the value increases. Many liquid detergents currently on the market have enzymes distributed in their composition.

To the best of the inventors' knowledge, all commercially available products] 111
7) at 8.5°F or higher.

Many enzyme-free liquid laundry detergents have a pH of 9.0 or higher. A high product pH is desired, both in concentrated form during neat pretreatment and in cleaning solutions used at concentrations of about 0.2%, since alkaline liquids are improved against fatty soils. This is because it exhibits excellent performance. If the pH of the cleaning solution is 8.5 or higher, improved washability against fatty stains can be achieved by saponifying fat to form soap. Improved performance against both protein and fatty soils is obtained with high pH liquids containing enzymes. Additionally, fatty soils lower the pH of the wash solution, so the p++ of the wash solution
Liquid detergents that resist deterioration of the water are preferred.

This resistance to lowering the pH of the cleaning solution in the presence of fatty soils stems from the buffering capacity provided by the detergent.

Since, it has been difficult to formulate proteolytic enzymes in high pH liquids and maintain acceptable enzyme stability over the long shelf life spent in manufacturing, distributing and selling the product. there were.

Liquid laundry detergents having some of the features of the present invention are disclosed in the patent literature.

Eida Patent No. 1590445 (Unilever, corresponding to U.S. Pat. No. 4,261,868) discloses that fossa 1111 (7,
5-]-1,0) Discloses the use of enzymes in liquid laundry detergents with stabilizing systems containing polyfunctional amino (arsenic compounds such as triethanolamine) and borax.

According to this document, the ratio of anionic surfactant to nonionic surfactant is 1.1 to 1:10. Example 1 is sodium tripolyphosphate, dimethylglycine and ^1c
It uses ulasc™ enzyme and has a p of 10.0.
It states that it has H.

European Patent No. 0080223 (Uni
ver, corresponding to U.S. Pat. No. 4,462,922)
The use of highly alkaline enzymes in liquid detergents with a stabilizing system comprising borax, reducing alkali metal salts and polyols and/or polyfunctional amine compounds is disclosed. 1) 11 of the composition is neutral, preferably 8.0
~10.0. US Patent No. 446
According to No. 2922, the composition can be adjusted to a value of 100% by adding a suitable buffer system. ? It is stated that 1111 of the previous V night is preferably 11 It smaller units than this with a modification in use of 19≦. US Patent No. 4
According to No. 462,922, reducing alkali metal salts are used to obtain effective enzyme-stabilizing compounds.

European Patent No. 0126505 (Unilever
, corresponding to U.S. Pat. No. 4,532,064) discloses the use of highly alkaline enzymes with maximum activity at pH 8-12 together with borax, reducing metal salts, optional buffer solutions, and polyols in liquid laundry detergents. Alternatively, the use of dicarboxylic acids in place of polyfunctional amine compounds is taught. The pH of the final composition is near neutral, preferably 7.5.
and can be buffered to values within this range by adding an appropriate buffer system. Is the pH of the washing water 1? Approximately 1.0% higher than this at a concentration in use of ≦. p 11 units higher.

1))1 in Example 1 is 7.5.

U.S. Patent No. 431,881.8 (LeLton et al.)
The use of enzymes in liquid laundry detergents with a stabilizing system comprising polyols, calcium and short chain carboxylic acids is disclosed. Mono-, di- and triethanolamines have pH
Can be used as a buffer. U.S. Patent No. 4:31881
According to No. 8, the possible product pH range is 65 to 10, with a preferred range of 7 to about 8.5 for a combination of enzyme stability and detergency.

Example X11IE of U.S. Pat. No. 4,318,818 is M
axaLase, surfactant, ethanol, formic acid 1-
liul, and triethanolamine (heavily used,
It states that ρ)I of 96 exists. Example X1llP
uses surfactants, ethanol, MaxaLase, sodium carbonate, and formic acid; 10.
0 of 1) 11.

European Patent No. 0080748 (Unilever)
, corresponding to US RFI Patent No. 4404+15) is
J'11 teaches the use of enzymes with a stabilizing system that includes liol (optional ingredient), alkali metal sulfite, and alkali metal pentaborate in the wood wash detergent. Pentaborates are best used in liquid compositions where dilution at the time of use provides a sufficiently alkaline pH for optimal cleaning power11).
It is stated that it provides a buffering effect under one condition. The pH of the wash solution when the composition is used is stated to be in the alkalinity range well above 8 when used (with modification) of about 1%.

Example 11t(6) has a pH of 11.36 and 1%
A composition containing a metaborate and an enzyme is disclosed such that the pH of the solution is 926 and the enzyme stability after two weeks is greater than 10-6°F. Other ingredients include the surfactant triphosphate builder.

European 'Admiral No. 0080748 states that cleaning solution pH
Although the company recognizes the importance of having a high The present invention provides pretreatment benefits over this European patent. Also, European Patent No. 0080748 uses pentaborate instead of tetraborate (borax) (page 2, line 5).

U.S. Patent No. 4652394 (I na + no
(R.A. Loike) teaches the use of enzymes in aqueous laundry detergents with an enzyme stabilizing system containing propylene glycol and borax. Rice ``V'+1 permission No. 46
No. 52394 is a high p
If you are not aware of the use of liquid.

In each of the above, the prior art patents jointly provide the benefits of improved pre-treatment and cleaning efficacy for fatty soils, as well as those necessary to remove enzyme-sensitive soils. It is clear that there is no recognition of at least one critical component that maintains enzyme activity.

With the desire to combine the properties of high alkalinity levels and the inclusion of enzymes in detergent products, pH 8,
A specially formulated alkaline protease enzyme has been developed to produce peak efficacy in wash solutions of 5 or more. Currently, many powder detergents contain high alkalinity sources and enzymes that are designed to function primarily in high +1 tl wash solution systems. Powdered detergents have therefore been able to offer consumers maximum cleaning benefits in two major ways. The problem in the past has been to combine these two highly desirable properties in a liquid detergent. In highly alkaline liquid detergents, enzymes are dissolved at high product pH (>9.0). It is known that a high product rol+ is detrimental to enzyme stability over long periods of time (often at elevated temperatures) as seen in conventional product storage. We have determined that enzyme stability is sufficient for effective decontamination.
We have realized a liquid detergent system that provides the above two performance benefits while maintaining the same characteristics.

The present invention stably incorporates enzymes into high 1) 11 liquid laundry detergents, thereby improving the detergency against enzyme sensitivity and fatty soils. The basic principle of the present invention is
The performance of proteolytic enzymes is improved by stably adding titratable alkalinity sources at specific levels with enzyme stabilization systems using glycols, calcium and/or borax (washing and pre-treatment). )
Good removal of fatty stains.

The present inventors have discovered the stable formulation of enzymes in combination with desirable liquid detergent ingredients in highly alkaline liquid laundry detergents. Many commercially available products include some of the features of the present invention, and while several products can be used in combination to provide many of these features, it may not be possible to obtain all of the benefits desired by the consumer. To date, no such liquid detergent is commercially available. These advantages include the convenience of liquids, the ability to better remove blubber stains in both wash and pretreatment applications, and the ability to efficiently remove enzyme-sensitive stains.

The present invention has 1) a stock solution pH of 9.5 or more so that fatty stains can be removed well by pretreatment, and 2) a pH of 0.000 to provide good cleaning power for fatty stains. .2% by weight) Solution pH' of 8.5 or higher at 3 degrees
, and 3) measuring up to p117 and t4 a 20 to obtain the buffering of the cleaning solution that is desirable for fatty soils.
at least 0 per g of product when calculated as % of
．． It has a titratable alkalinity of 5% by weight and 4
) contains effective levels of enzymes for decontamination, including at least one alkaline protease capable of achieving effective decontamination when used in cleaning solutions of pH 8.5 or higher; 5) Ingredients selected from the group of known enzyme stabilizers including glycols, boron compounds, calcium and polyfunctional amine compounds so that sufficient stability is maintained for effective removal of contaminants during use. The present invention relates to liquid laundry detergents containing effective enzyme stabilizing systems, alone or in combination.

As detailed below, a preferred system that achieves all of the above features includes primarily anionic and nonionic surfactants.
an alkalinity system employing a level of up to about 40% by weight of an active system, about 5 to about 20% by weight of a soluble hilder (e.g., citrate), and about 1 to about 6% by weight of one or more alkanolamines; and Alcalase(TM), 5avi
nase (trademark), Maxaca l (trademark) or E
an enzyme system comprising at least one alkaline protease, such as speraSe™, and an enzyme stabilization system comprising 1 to about 8% glycol, boron compound j, preferably about 1 to about 8% borax; 0.001 to 0.1% by weight, calculated as alkaline earth cations, of an alkaline earth salt, such as an alkaline earth cation source obtained from CaC12). Formate is not a necessary ingredient in the compositions of the present invention. Similarly, the compositions of the invention may be substantially or essentially free of phosphate. Essentially phosphate-free means that the phosphorus content (as phosphorus) is less than 0.5%°F. Preferably, compositions of the invention exhibit at least 25% of their initial enzyme activity after two weeks at 105°F.

Suitable liquid detergents of the present invention may further include a dorotrope for product stability, one or more fluorescent dyes and/or bluing agents to brighten the batter, coloration for product appearance. and/or opacifiers, fragrances to provide an acceptable product odor during wear and tear. Advantageously,
The detergent of the invention may be an isotropic liquid, ie a single phase liquid.

The basic principle of the present invention is the stable formulation of the above-mentioned ingredients into a liquid laundry detergent that provides effective enzymatic stain removal with excellent fatty stain removal ability in both wash and pre-treatment applications. .

In the description herein, unless otherwise specified, pH represents a value measured at 25°C.

The liquid laundry detergent of the present invention contains a surfactant (anionic, nonionic, cationic, bipolar or amphoteric or mixtures thereof), bilgoos for water softening, alkalinity/balancing agents to maintain p++ in neat and dilute solutions during washing, solubilizers for phase stability of the active agent in solution, or Hydrotropes, enzymes for decontamination (proteases and optionally amylases, cellulases, lipases or mixtures thereof), polyhydric alcohols and/or boron compounds to maintain enzyme activity after storage, whitening of clothes Contains fluorescent whitening and brightening agents, softening agents, foam suppressants, appearance modifiers (such as thickening or opacifying agents, bluing agents and coloring agents), disinfectants, fragrances and preservatives. Optionally, performance enhancers may be added, such as bleaches (chlorine or oxygen bleaches), stain separators, anti-resoiling agents or soil clouding agents, solvents, or minor performance-enhancing components of the pond. Each of these optional ingredients will be explained in detail below.

Although cationic, zwitterionic or amphoteric surfactants can be considered acceptable for use and fall within the scope of the present invention, washing i7J 11'! It is more convenient to use anionic or nonionic surfactants and mixtures thereof in the formulation of liquid detergents. Particularly preferred are ternary surfactant systems of a linear alkylbenzene sulfone, a linear ether sulfate, and a xylated alcohol nonionic surfactant.

Suitable zwitterionic and amphoteric surfactants are described in U.S. Pat.
No. 28039, suitable cationic surfactants are US [11
It is described in Japanese Patent No. 4497718, and the disclosure contents of these patent documents are included in this document. Hereinafter, suitable anionic and nonionic surfactants will be explained in more detail.

Anion Anionic surfactants include both soap-based detergents and synthetic detergents6 Synthetic anionic detergents are broadly defined as approximately 8
Defined as a water-soluble salt of an organosulfur reaction product having in its molecular structure an alkyl group containing about 22 carbon atoms and a group selected from the group consisting of sulfonic acid and sulfuric acid ester groups Can be done. Such surfactants are well known in the detergent art and are available from 5cbuarLz, Perry
and “5surface 8active” by Bercb.
8 gents and detergents”
, Vol.

It is described in H. More useful synthetic anionic surfactants include alkyl, alkylaryl or argenyl sulfonates, and alkyl and alkylene ethoxy sulfates.

Suitable alkylaryl sulfonates include, for example, alkali metal or ammonium or alkanol ammonium salts of alkyl aromatic sulfonates, such as higher alkylbenzene sulfonates containing 10 to 16 carbon atoms in the alkyl group and having a straight-chain or branched armor. Can be mentioned. The average number of carbon atoms in the alkyl group is about 10 to
Particularly useful are linear straight chain alkylbenzene sulfonates, such as those having a molecular weight of about 14%. Other useful anionic sulfonates are olefin sulfone-1-, paraffin sulfone-1-, alkylglyceryl sulfonates, including long chain alkanesulfonates, long chain hydroxyalkanesulfonates or mixtures thereof, or especially linear It is a mixture with alkylbenzene sulfonate.

Suitable alkyl sulfates include those in which the alkyl chain contains about 10 to about 18 carbon atoms, and the sulfate is an alkali metal (e.g., sodium or potassium) or an ammonium or alkanol ammonium compound (such as mono-, di-, or triethanol ammonium). Examples include those formed by cations forming solubilizing salts such as salts. A suitable alkyl ether [~xysulfate] has the formula 1tO
(C21LO). 501M, where R is preferably alkyl having a chain length of C1° to CIG, n is on average from 0.5 to about 10, and H is as described above for alkyl sulfates. It is a cation that forms solubilizing salts.

Another class of anionic surfactants useful in the practice of this invention, alone or in combination with other surfactants, are soaps. Sodium or potassium soaps are generally used with soaps derived from a fatty acid component or a mixture of saturated and partially unsaturated fatty acids in the C8 to C26 chain length region. The source of fatty acids is conventionally a blend of coconut oil and tallow, but may be utilized from other sources such as palm kernel oil, peanut oil or sunflower seed oil. Of course, the liquid detergent of the present invention does not necessarily have to contain soap.

The amount of the anionic surfactant used is about 1 to 1% of the total formulation.
It is approximately 30% by weight. Suitable anionic surfactant usage levels are from about 2 to about 20%, and a single anionic surfactant or a mixture of the above anionic surfactants may be used.

Mixtures of anionic surfactants are optimal where each level is from about 4% to about 15% and the total level of anionic surfactant is from about 8% to about 30%.

Niin 1 Suitable nonionic surfactants have the formula RO (C21140),
O1+, where R is a 08-C18 carbon chain or a C6-C12 alkyl phenyl group, and n is about 2 to about 12. Specific examples of suitable linear linear alkyl nonionic surfactants include the various Neodo 1 designations (S
HellChemical), the various ΔIronic names (Vista) and the various Tergijo 1 names (Union Ca).
This type is commercially available as rbide). The amount of the nonionic surfactant used is about 1 to about 20% by weight of the entire formulation.
It is. The preferred nonionic surfactant usage level is approximately 3
to about 12% and may consist of a single nonionic surfactant or a mixture of the above nonionic surfactants.

u[f2 The compositions of the invention optionally contain builders.

Suitable builders useful in the present invention include organic and inorganic builders. Examples of suitable inorganic builders are alkali metal ortho-, pyro- or tripolyphosphates, silicates or crystalline or amorphous zeolites I. Examples of suitable organic building blocks include ethylene thiamine
Acids, nitrile: alkaline salts of acids and polycarboxylic acids (eg citric acid). Other examples of suitable organic building blocks include carbonates, succinates, and maleic and acrylic acid polymers and copolymers.

The amount of the builder used is about 05-25% by weight of the total formulation. Preferred builder usage levels are about 3% to about 25%
, particularly from about 5% to about 20%, and a single builder or a mixture of the above builders may be used.

Arnoli 611''/:P''1 Many of the bilgu constitute a source of alkalinity in addition to their primary function of softening the hardness of water;
In addition to builders, alkalinity agents are often used to provide an alkalinity reserve source to maintain the soil's moisture content and to buffer the acidic components of the soil.
ir) is used. Suitable alkalinity sources that can be used within the scope of the present invention include alkali metal hydroxides,
Included are silicates, carbonates, and alkanolamines selected from the group consisting of monoethanolamine, jetanolamine, triethanolamine, and mixtures thereof. The amount of alkalinity agent used is about 0.1 to about 10% by weight of the total formulation. Suitable levels of alkalinity used range from about 0.5 to about 82≦, and may consist of a single alkalinity source or a mixture of the above alkalinity agents. The alkalinity agents of choice are alkanolamines, either singly or as a mixture, with total levels of alkanolamines ranging from about 1 to about 6% by weight of the total formulation.
It is. Monoethanolamine is particularly preferred. Although alkanolamines are preferred ingredients, the liquid detergents of the present invention may be amine-free.

The total titratable alkalinity from all sources in the composition of the invention is at least 0.5% by weight per g of product, measured up to p117 and calculated as % Na2O.

Boron compounds useful in the present invention include boric acid, boron oxide, and alkali metal borates. Typical examples of alkali metal borates are sodium and potassium, or
-, pyro and metaborate, polyborate and borax. A preferred alkali metal borate is borax, which is a tetraborate commercially available as the pentahydrate or decahydrate. The amount of boron compound used is 0.1-10% by weight of the entire formulation, and borax pentahydrate is preferred (the level of use is about 1-8% by weight). .

It is not necessary to add pentaborate to the compositions of the invention.

The enzymes to be included in this compound can be proteolytic, starch-degrading, thimble-degrading and cellulolytic enzymes, and mixtures thereof.

A particularly suitable enzyme is obtained from a Bacillus strain, 7
．． It is an alkaline protease with maximum activity throughout the pH range of 0-12.0. Enzymes are granules, malus＼(
+n a r u +n e s ), granules, or any other suitable form may be used, but it is more convenient to add it to a liquid detergent in a fluid form such as a liquid or slurry. . Specific examples of proteolytic enzymes suitable for use in the present invention are available from Novo Industries, Copenhagen, Denmark under the tradenames Δ1culase(TM), 5avinase(TM).
, and products marketed as Esperase™ and products sold by Int., Rijsu+ijk, The Netherlands.
Maxatase™ and Max commercially available from national BiosynLheLics
aca l (trademark). 5avinaSe(TM), Maxacal(TM), and Alcalase(
Trademark) is particularly suitable.

A specific example of an amylase enzyme suitable for use in the present invention is N
Termamyl, commercially available from ovo and Interna, Rijsu+ijk, Netherlands.
tional [1 Maxamyl commercially available from iosynLhetics.

The amount of enzyme used in the liquid composition depends on the concentration of active enzyme in the particular product, but generally ranges from about 0.001 to about 10
It is at the level of % by weight. - In a preferred system, alkaline protease is used, optionally in combination with amylase, and the total usage level of enzyme is about
It is approximately 5% by weight. The activity of the enzyme in the 7-night body composition of the invention is preferably 0.001 kg Nov/g of product.
a protease unit (KNPU) to 1 KNPU.

The INovo protease unit is an enzyme that hydrolyzes dimethyl casein into peptides (50°C and pH 8.3).
(determined by reacting the primary amino group with trinitrobenzene sulfonic acid at an initial rate corresponding to glycine of 11 nmol/min). Roughly speaking, 3KNPU is equal to about 1Δns o n 4j. 1
KNPU roughly corresponds to 80,000 alkaline Delft (Δ1 kaline Delft) units. The protease used in the present invention has a minimum value of 0,001 KNPU.

Polyols useful within the scope of the present invention include polyols having from 2 to 6 hydroxyl groups. Preferably the polyol contains 1 to 6 carbon atoms.

Typical examples are polyhydric alcohols, ethylene glycol, propylene glycol, dipropylene glycol,
and glycerol. Suitable polyol usage levels are from about 0.1% to about 20% by weight of the total formulation, with optimal levels being from about 1 to about 826% of the formulation as polyol alone or as a mixture of polyols.

7/L Yobei 2Lf, 11th verse - Any water-soluble alkaline earth salt may be used as the cation source in the solution. Suitable alkaline earth salts include calcium and magnesium salts such as chlorides, sulfates and acetates.

Calcium salts are the alkaline earth salts of choice, and their usage levels are from about 0.0001% to about 1%, with a preferred range of about 0.0001% to about 0.01% by weight based on the weight of Ca+4 ions. It is. The levels used are higher than any metal ion present in enzymes.

Hydrotrope Tree The term human Ij I-rope as used herein refers to a substance that water-solubilizes the primary surfactant used in the composition. Hydrotropes suitable for use in the present invention include ammonium or alkali metal salts of benzene sulfonic acids and mono- or dialkyl substituted benzene sulfonic acids in which the alkyl chain contains 1 to 3 carbon atoms.

Alkylbenzene sulfones 1~ include 1~luene, ethylbenzene, isopropylbenzene and 0-lm-
and l] -'r silene sulfonate and mixtures thereof. Hydrocarbons suitable for use in the present invention also include short chain alcohols having 2 to 6 carbon atoms and mixtures thereof. The amount of the hydrotrope used is 1 to 15% by weight of the total formulation. Suitable for no mud l ~ Rope usage level is about 2-10%
A single hydrotrope or a mixture of the hydrotropes described above may be used.

Suitable fluorescent whitening agents for use within the scope of the present invention include:
Diaminostilbendisulfonate cyanuric chloride derivative (DAS/CC) is mentioned.

The main components of the DΔS/CC type fluorescent dye "(4,4'bis[4anilo-6-substituted-1,3,5-1~lyazine-2
-yl) aminocostilbene-2,2° disulfonic acid,
or an alkali metal or alkanolamino salt thereof, where the substituent is morpholino, hydroxyethyl, methylamine, dihydroxydiethylamine or methylamine. The structure before the acid form is shown below.

The optimal fluorescent whitening agent used is Tinopal 8MS
(Ci to a-GeiI?y) where R1 and R2 are morpholino or Tinopal 5BM (Ciba
-Geigy) where R (and R2 is hydroxyethylmethylamino), or Tinopal UN+
“Eight (Ciba-(:eigy)), like R1 and R
Fluorescent whitening agents such as those in which 2 is dihydroxydiethylamine. Fluorescent whitening agents suitable for use in the present invention include the trade name Tinopal RBS (Ciba-Geig
Ph
oru+it, eB11C (Mobay)), or distyrylbiphenyl type (Tinopal CBS-X (C
iba-GeiHy)) fluorescent whitening agent is used. The amount of the fluorescent whitening agent used is about 0.001 to about 2 of the total formulation.
Weight%. The preferred fluorescent whitening agent usage level is approximately 0.0
1 to about 0.52≦, and a single fluorescent whitening agent or a mixture of the above fluorescent whitening agents may be used.

"minor" Jk min - A large number of heavy detergent additives (strictly speaking, "trace additives (min.
or additives) are suitable for use within the scope of the present invention. These additives are ingredients that, although added in small amounts, can significantly contribute to the performance and marketability of detergent products. Minor ingredients that may be used in the present invention include foam suppressants, thickeners (e.g. cellulose ethers), opacifiers (e.g. polystyrene latex), blue tints, colorants, anti-counterfeiting agents, processing aids and fragrances. Additionally, optional performance-enhancing ingredients, often in large amounts, may be included, such as bleaching agents (e.g. inorganic peroxy compounds and activators), anti-staining agents, anti-restaining agents or soil suspending agents and Any performance enhancing component of the pond may be mentioned.

Panron” 1 tone 1 These washing i? a The method for preparing the JT1 liquid detergent meter includes two mixing steps: main mixing and pre-mixing. The main mixture includes batch water and all or a portion of the hydrotrope, builder anionic surfactant, enzyme stabilizing system, and minor ingredients (eg, colorant shade). These ingredients are stirred and heated (directly or via the heat of neutralization of the anionic surfactant) to a temperature below about 140 tl. Optionally, a portion of the alkalinity/cherry Flit agent may be added to the main batch.

Yonan mixtures contain nonionic surfactants and fluorescent dyes, optionally hydrotropes and certain Ia,! It may contain part or all of an fE component (eg, a foam suppressor). According to a preferred embodiment, the premix contains part or all of the alkalinity agent. Heat the premix to a temperature of about 140-160°C while stirring to disperse the fluorescent dye. The premix is then added to the main batch mix with sufficient agitation to obtain an even mixture. The batch mixture thus prepared is then cooled to below 100 ℃ and the enzyme and fragrance are added.

Chikatsu Town The following compositions were used to illustrate the present invention. All ingredients are expressed as % by weight based on 100% active material unless otherwise specified in 1.

11"L NaLΔS (linear alkylbenzene sulfonic acid salt whose alkyl chain length is equal to the average number of carbon atoms 11) NaLES (downwards 3 moles of ethylene oxide and 1 mole C
Sulfated condensate sodium salt with l2-Cl3 alcohol) Ethoxylated C with an average number of l xylate groups of 97 moles
l2-CIS alcohol ethanol 1 heliethanolamine monoethanolamine propylene glycol borax 5 aqueous phase calcium ion (+2) sodium citrate dihydrate alkaline protease water and other ingredients 2 0.8 3.06 0.01 1.0 up to 100 1, Novo Laboratories commercial product 5
avinase 8. OL (trademark).

2. Contains colorants, fragrances, fatty acids, opacifying agents and fluorescent whitening agents.

Comparative Compositions 1 and 2 are commercial laundry enzyme-containing liquid detergents believed to have the ingredients and levels listed. Comparative composition 3 is a commercially available builder-containing liquid detergent that does not contain enzymes.

〃Zai Qi Chun NaLΔS 8.9 3.
6 17NaLES (approximately 25 ethyleneoxy units>
1.2.8 0 001□-CI+fatty acid potassium j, salt 13.1. Ethoxyl having an average of 8 to 9 1-xy-1-groups per molecule of OO (H-C12-C14 alcohol 5.9),
6.5 7 Monoethanolamine
10 0 2 propylene glycol
4.2 0 0 Sodium citrate dihydrate 6
．． 0 0 10 Cationic surfactant
T, o o.

Ethanol 8.5 5
．． 1 0 alkaline protease'' 0
．． 52 0.49 0 amylase”
0.32 0.15 0 Water and other ingredients up to 10oz 5100$
Up to 6100$73, Novo 1. abora
tories commercial product Alcalase 2.51, (
trademark).

Novo La with an activity of 4,134KNLl/g
Based on the commercial product Ter+namy (trademark) from boratories.

5 Contains calcium chloride, sulfur and lithium formate, colorants, fragrances, EDTA, and fluorescent whitening agents.

6 Contains sodium carboxylate, polymer, colorant, fragrance and fluorescent whitening agent 3.

7. Colorants, fragrances, fatty acids, fluorescent whites (including astringents and opacifiers).

Prior to the present invention, high I' without such a builder
It is believed that liquid detergents containing l+ (8.5 to 9.0 or higher) enzymes have not been commercially available, mainly due to insufficient enzyme stability. The enzyme stability of liquid laundry detergents was tested by storing them at elevated temperatures for several weeks. Enzyme stability was expressed as the percentage of initial enzyme activity maintained after such storage conditions.

As shown below, Composition I has a higher p+
1 (10.1 compared to 8.3 for Comparative Composition 1), it has better stability than Comparative Composition I.

■ 1 (Comparison) Protease susceptibility test By washing the cloth, the efficacy and stability of the enzyme can also be tested. Tcrg-
o-LomeLcr (registered trademark) (U, S, Test
Hardness of p + n (2 Ca
: IMg) was used to wash the trial cloth containing casein (dry milk), and the results shown below were obtained. The detergency was obtained from the reflectance R measured on uncontaminated fabric, contaminated fabric, and washed fabric.

■ 4 weeks at room temperature 105°F 1 (specific axis) 4 weeks at room temperature 105°F 2 (comparison) 4 weeks room temperature 3 (comparison) The performance of the composition was equal to or better than a comparative composition maintained at room temperature. 105 after 4 weeks, compared to
The performance of 11211 Product 1 was less than that of Comparative Composition 3, which did not contain the enzyme.

Higher p 11 washes) M conditions and higher alkaline t'
A product that confers A fE ability is desirable because currently commercially available alkaline proteases
for two reasons: it performs well in wash liquors with t; t, the dilution of the product in water is 0.2% by weight resulting in a pH of 85 or higher; t)j: Kt
Such a formulation is desirable.

This dilution is a typical wash dose for most liquid laundry detergents.

Compositions ① to ① are other embodiments of the present invention. Both of these compositions have the same surfactant and builder system as Composition I, but other ratios and levels can be used with similar results. For comparison of the compositions, all other ingredients were the same as in 4. Product 3. Comparative composition 4, which does not fall under the present invention, is also shown.

■・Reethanolamine Monoethanolamine Propylene Glycol Borax Pentahydrate Calcium Ion Alkaline Protease Wooden Jujube Dim 1 Shuppara H L Dish IVVVI Ri K 3.062.702.302.301,532.301
．． 530.0+, 0.010.010.010.01
0.010.011.0 ], o i, 0 1.0
+, 0 1.0 1.0*Novo Labora
tories commercial product 5avinase 8. OL (trademark).

Many commercially available alkaline proteases are
It is known that 1 higher than 8.5 has optimal efficiency. It is beneficial to include sufficient alkalinity reserve in the composition to maintain a relatively high 11 when diluted to about 0.2% aqueous solution. 0.2% solution 0.1O
N(7) 11Cl, pH 7, 2, then 21C
Buffering capacity was determined by determining the number of moles of N a 20 that neutralizes. The weight of Na2O was divided by the weight of product (2.00g per 1 p titration) and then multiplied by 100 to obtain the percentage of Na2O in the formulation. Table 71 shows the values for Compositions I to ■ and Comparative Compositions 1-4.

Dark Blue Daimono Bandan 1 (Hiko Koko) 3 Knol) (Enzyme-free) Layer α sub-8.3 6.8 10.4 9.7 Kamedojin pH 7. Alkalinity Preliminary up to oo 110 Rapid Ejection -- 0,37 0,82 2,0 0,93 0,23 8 Alkalinity Preliminary of Comparative Example 2 (11u is soluble
is less than 7, so it is O.

Alkalinity reserve is most important for stains containing Tienmu oil and fatty acids. These stains degrade at high pH, resulting in a lower pH of the wash solution.

A high level of alkalinity, such as in the compositions of the invention (I-■) and the enzyme-free liquid (3), is very beneficial for such reactions. Table 5 shows fatty acids/vacuum 117 divided by 1
The table confirms this trend, far from showing the effectiveness of these detergents on shallow dust.

Fifthly, the effect of the cleaning solution I]11 is not as strong as the enzyme efficacy, and the effect of the cleaning solution is cold, in-test! This is clearly shown in the washing results obtained by application. In the casein test fabric, 1) and 11 did not substantially change in the fatty acid fabric.

1 (Comparison) 2 (No) 3 (Tsuno) ■ ■ ■ ■ ■ ■ 4 (Comparison) Table 5 Fat, Fatty Acids / Shinjiya "Sai"Yo-sawa" 1 艮L''L It is clear from these data that the composition I of the present invention
~V is significantly better in 'IJ than the commercial product for at least one of the test fabrics and equivalent for the other. These formulations represent preferred compositions of the present invention. Composition■
～■ shows better performance than commercially available products, but low p near neutrality
Unlike undesirable liquids with H, these enzyme-containing stock solutions have a high pH. A high stock solution pi+ is important for removing fatty soils in pre-treatment situations. Comparative Composition 3 has a substantial alkalinity reserve, but lacks enzymes and does not provide significant cleaning effect on casein test fabrics. Comparative composition 4 does not contain the tm alkaline alkaline powder (@) of the present invention. Comparative composition 4 has average enzyme cleaning performance, but has poor results on the fatty acid/vacuum cleaner dust test cloth. Although Composition 4 is significantly inferior to the compositions of the present invention, it is superior in many respects to Composition 2, which is one of the commercially available enzyme products.

Only Composition ① and Comparative Composition 3 have an undiluted solution, +1 of 9.5 or more, a pH of 082% aqueous solution of at least 8.5, and an alkalinity of ρI+ 7, 0 of 0.5% Na.
Over 2O'5.

Composition 3 contains no enzyme, but if enzyme were added the activity would drop to near zero after only a few days of storage. Compositions I-III are embodiments of the present invention having a unique combination of high alkalinity, high alkalinity reserve, and enzyme potency.

Compositions ① and 1K having the following compositions were prepared using sodium carbonate as an alkalinity source.

枇逼U-gobian" L LIX'- NaLΔS (alkyl chain length is average carbon Linear alkyl with atomic number equal to 11 benzenesulfonic acid sodium salt) NaLES (average 3 moles of ethylene oxide and 1 mole Cl2-Cl3 Sulfation with alcohol Shrinkage 1~lium salt) average ethoxylate 91 mol of polyoxylated C1. -C15 alcohol ethanol l Heliethanolamine monoethanolamine Propylene glycol Borax pentahydrate Calcium ion (''2) sodium carbonate 1 helium citrate, 2 aqueous phase alkaline protease 9 water and other ingredients 0, 01 1, 0 1, 0 up to 100 0,8 0, 01 1, 0 up to 100 9, Novo Laborator mark).

10, colorants, fragrances, Contains inhibitors.

The results of measuring the alkalinity of Compositions (1) and (2) are shown below.

Yuzu clan 糎 Egg number 凰 Qiu pu shi pu 1 Usujiki no yo■
9.8 8.911X10.2
9.16 Preliminary alkalinity up to pH 7, oo - ■. 09 1,55 Enzyme stability test results showed that compositions ~1 and IX were 1! at high temperature! ? It was found to have good stability after storage (4 weeks at 105°F).

It should be understood that the specific examples listed above are merely illustrative. Non-limiting modifications may be made to the embodiments described herein without departing from the disclosure, including all permutations and subcombinations of features as described herein and in the claims. It is also possible to add

Claims (23)

[Claims] (1) A liquid detergent composition containing a surfactant, an alkaline protease enzyme, and an enzyme stabilization system, the composition comprising:
(a) has a stock pH of 9.5 or higher; When diluted at a rate of 8
．． (c) has a titratable alkalinity of at least 0.5% per gram of product when calculated as % Na_2O and titrated to pH 7; (d) ) i) polyols, ii) boron compounds selected from boron oxides, boric acids and alkali metal borates, iii) calcium ions, iv) polyfunctional amino compounds, and mixtures thereof. A liquid detergent composition comprising an enzyme stabilizing system and (e) having a water content of 5 to 80%. (2) Claim 1 further comprising at least 0.2% by weight of a monoethanolamine buffer.
Liquid detergents listed in. (3) The liquid detergent according to claim 1 or 2, wherein the surfactant contains an anionic and nonionic surfactant in a ratio of 1:1 to 10:1. (4) The liquid detergent according to any one of claims 1 to 3, wherein the pH of the stock solution is about 10 or more. (5) The liquid detergent according to any one of claims 1 to 4, which is in the form of an isotropic liquid. (6) The protease is Alcalase (trademark), S
avinase(TM), Maxatase(TM),
Liquid detergent according to any one of claims 1 to 5, characterized in that it is selected from the group consisting of: and Maxacal™. (7) A liquid detergent according to any one of claims 1 to 6, characterized in that the protease is selected from the group consisting of Savinase(TM) and Maxacal(TM). (8) Liquid detergent according to any one of claims 1 to 7, characterized in that the formulation is essentially free of phosphates. (9) The liquid detergent of any one of claims 1 to 8, further comprising about 3 to about 40% builder. 10. The liquid detergent of any one of claims 1 to 9, comprising at least 0.2% monoethanolamine buffer and about 3 to about 40% builder. (11) Claims 1 to 1 characterized in that it has a protease activity of 0.001 to 1 KNPU per g of product.
Liquid detergent according to any one of Item 0. (12) The surfactant according to any one of claims 1 to 11, characterized in that the surfactant comprises an anionic surfactant selected from the group consisting of alkylaryl sulfonates and alcohol ethoxy sulfates. liquid detergent. (13) The liquid detergent according to any one of claims 1 to 12, wherein the stabilizer contains borax or boric acid. (14) The liquid detergent according to any one of claims 1 to 13, wherein the stabilizer contains calcium ions. (15) The liquid detergent according to any one of claims 1 to 14, wherein the stabilizer contains borax. (16) Liquid detergent according to any one of claims 1 to 15, characterized in that the stabilizer comprises a polyol selected from the group consisting of propylene glycol, ethylene glycol, glycerin and mixtures thereof. (17) a) contains 10-25% anionic surfactant, b) contains 2-12% non-ionic surfactant, c) 0.5-10% monoethanol, contains diethanolamine, triethanolamine or a mixture thereof; d) has a stock pH of 9.5 or higher; and e) has a solution pH of 8.5 or higher at a working concentration of 0.2% by weight. f) contains from 3 to 25% builder; g) has a titratable alkalinity of at least 0.5% by weight per g of product, measured to pH 7 and calculated as % Na_2O; h) contains 1-10% of a polyhydric alcohol selected from the group consisting of propylene glycol, ethylene glycol, and glycerin; i) has a pH of 8.0 at a working concentration of 0.2% by weight; 0.00 per gram of product that can be decontaminated in more than 5 washes
Contains levels of enzymes effective for the removal of contamination, including at least one alkaline protease with an activity of 1 to 1 KNPU; j) Contains 0.1 to 10% borax, boric acid or mixtures thereof; The liquid detergent composition according to claim 1, characterized in that: k) it is in the form of a heavy liquid detergent having a water content of 5 to 80%. (18) The liquid detergent according to claim 17, characterized in that it contains 0.2 to 5% by weight of monoethanolamine. (19) a) contains 1 to 60% by weight of one or more surfactants, b) has a stock pH of 9.5 or more, and c) has a working concentration of 0.2% by weight. has a solution pH of 8.5 or higher; d) has a titratable alkalinity of at least 0.5% by weight per g of product when measured to pH 7 and calculated as % Na_2O; e ) containing effective levels of enzymes to remove contaminants, including at least one alkaline protease capable of removing contaminants in a wash solution with a pH of 8.5 or higher; f) i) polyvalent; alcohol, ii) a boron compound selected from the group consisting of boron oxides, boric acid and alkali metal borates, iii) calcium ions, and iv) mixtures thereof. g) in the form of an amine-free heavy liquid detergent with a moisture content of 5 to 80%, the heavy detergent having an initial Liquid detergent according to claim 1, characterized in that it exhibits at least 25% of enzymatic activity. 20. The heavy duty liquid detergent of claim 17, further comprising about 0.5% to about 25% alkali metal carbonate. 21. The heavy duty liquid detergent of claim 17, further comprising about 0.5% to about 25% alkali metal silicate. 22. The heavy duty liquid detergent of claim 19, further comprising about 0.5% to about 25% alkali metal carbonate. 23. The heavy duty liquid detergent of claim 19, further comprising about 0.5% to about 25% alkali metal silicate.