JPS59140300A - Aqueous liquid detergent composition - Google Patents

Abstract

The invention pertains to aqueous liquid detergent compositions having improved non-corrosive properties which comprise an effective amount of silica having a surface area greater than 200 m<2>/gram. The inclusion of silica provides good non-corrosive properties both in respect to metal and enamel surfaces.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to liquid detergent compositions, particularly aqueous liquid detergent compositions having improved non-corrosive properties.

Anti-corrosion is included in the detergent composition to counteract the corrosive and discoloring effects of the cleaning liquid on the metal or enamel parts of the cleaning machine and thereby prevent deterioration of machine performance or discoloration of textiles in contact with such corroded parts. It is desirable to include agents.

Aqueous liquid detergent compositions containing corrosion inhibitors are known in the art. Commonly used are soluble silicates such as metasilicates, orthosilicates and sesxylilicates. Apart from their corrosion-inhibiting action, such compounds provide liquid detergent compositions with a highly alkaline environment, which is not always a desirable situation, especially if alkali-sensitive ingredients are present in such compositions. That's when you use it. Further added corrosion inhibitors mentioned in the detergent technology section include sulfides, nitrides, carbonates, silica or organic compounds such as pesozoates. 1. Establishing a critical concentration of dissolved silica in the wash water It has now been discovered that the corrosive effects of aqueous liquid detergent compositions can be significantly reduced by incorporating such types of silica in such amounts as to reduce the corrosive effects of aqueous liquid detergent compositions.

The present invention therefore provides aqueous liquid detergent compositions having improved non-corrosive properties that include conventional detergent ingredients and an effective amount of silica of the type defined below.

It has now been found that in order to achieve optimal anti-corrosion protection, silica must be present in dissolved form in the cleaning fluid at a concentration of at least 120 ppm by weight and preferably 150 ppm by weight. Therefore, in accordance with the present invention, to provide the required amount of dissolved silica in the cleaning liquid to ensure adequate anti-corrosion protection, generally from about 1 to 10%, preferably 1.5% by weight of the liquid detergent composition. Silica will be incorporated into the liquid detergent composition in an amount corresponding to from up to 5% by weight and most preferably from 2 to 4% by weight, and this amount will be at a product dosage of 109/cm during cleaning. intended to be used.

If a liquid detergent composition is formulated with a preferred in-cleaning product dosage different from 109/cm, the amount of silica to be incorporated to achieve adequate anti-corrosion protection will therefore be The amount must be adjusted to correspond to the range as specified for 10'll'/product dose.

The silica to be used in the present invention should have a surface area of greater than 200 m2/g and preferably greater than 350 m2/g or even 500 m''/9. The upper limit of the surface area is critical. Although not a major factor, the surface area typically ranges up to about 1200 rrF'/g.

Generally such silica has a particle size of less than about 30 nm, particularly less than about 25 nm. Preferably the particle size is less than 20 nm or 10 nm
Even. There is no critical low limit for particle size; the low limit is constrained by other factors such as manufacturing practice, etc. Generally, commercially available silica has a particle size of 1 nm or more.

Suitable forms of silica include precipitated silica, amorphous silica such as pyrogenic silica, silica gels such as silica, )fk, Ki40 gel and Aeroglu, or pure crystalline forms of quartz, lepidolite. or contains cristobalite, but
Silica in amorphous form is preferred.

Suitable silicas are readily available commercially.

They are, for example, Aerosil 380 (Degu
ssa Corp, N.J., USA), Cab-0-Sil M5 (Cabot C
orp, , Ill, USA), Tixos
il 38A (SI Chimie, Franc
e) and Ga51l 200 (crosfi
sold under the registered trade name ela (from the UK).

The liquid detergent compositions of the present invention contain as an essential component an active detergent material, which comprises the alkali gold S of CIO-024 fatty acids.
- or alkanolamine soaps, including polymerized fatty acids, or anionic, nonionic, cationic, zwitterionic or amphoteric synthetic detergent materials, or mixtures of any of these. Anionic synthetic detergents are sulfate- and sulfate-type synthetic detergents. Those examples are C
9-02o Alkyl benzene sulfate salts (
(including sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts), C8-'C"22 primary or secondary alkanes sulfonates, C8-024 olefins
Sulfonates, e.g. British Patent Specification Drugs 1.082.1
Sulfonated polycarboxylic acids prepared by sulfonation of the thermal decomposition products of alkaline earth metal citrates as described in No. (contains up to moles of ethylene oxide)
The second example is Schwartz, Pe.
Described in "Surfactants and Washing" by J. R. R. R. and Berch, "Surfactants and Washing"*11'J (Volumes I and II), Medium Pressure.

Examples of non-ionic synthetic detergents are condensation products of ethylene oxide, zolopyrene oxide and/or butylene oxide with C8''01B alkylphenols, C3-C, primary or secondary aliphatic alcohols, CE-A18 fatty acid amides. Yes: Further examples of non-ionic detergents include tertiary amine oxides and one C8'''018 aryal chain and two c
l''' Contains condensates with C3 alkyl chains.

The above references also describe further examples of nonionic detergents.

Ethylene oxide and/or present in the above non-ionic detergents
Or the average number of moles of propylene oxide varies from 1 to 60; mixtures of various nonionic detergents can also be used, including mixtures of nonionic detergents and highly alkoxylated products.

Examples of cationic detergents are quaternary ammonium compounds such as alkyl dimethyl ammonium halokenonides.

Examples of amphoteric or zwitterionic detergents are N-alkylamino acids, sulfobetaines and condensation products of fatty acids with protein hydrolysates, but because of their relative cost they are usually combined with anionic or nonionic detergents. used. Mixtures of various types of active detergents can also be used;
And mixtures of anionic and nonionic detergent-active compounds are preferred. Soaps (in the form of their sodium, potassium, and substituted ammonium salts, such as salts of polymerized fatty acids) may also be used, preferably with anionic and/or nonionic synthetic detergents.

The amount of active detergent material is from 1 to 6% by weight, preferably from 2 to 40% and particularly preferably from 5 to 25%.
change by. If soap is included, its amount is from 1 to 40% by weight.

Although not essential, the liquid compositions of the invention preferably also contain up to 60% of suitable builder substances, such as sodium, potassium and ammonium or substituted ammonium birow and tripolyphosphates, -ethylenediamine tetraacetate, -nitrilotoli acetate, -ether polycarboxilade, -citrate, -carbonate, -orthophosphate,
Including zeolite, carboxymethyloxysuccinate, etc. What do you particularly like? rephosphate builder salts, nitrilotriacetates, citrates, zeolites, and mixtures thereof. Generally the builder will be present in an amount of 1 to 60% by weight of the final composition, preferably 5 to 5% by weight of the final composition.
Present in amounts up to 0% by weight.

The amount of water present in the detergent composition of the invention ranges from 10 to 70%
Varies up to % by weight.

Other customary substances can also be present in the liquid detergent compositions of the invention, for example sequestering agents such as ethylenediaminetetraphosphonic acid; alkali metals - chlorides, -bromides, -nitrates and -sulfates. non-pilder electrolytes such as sodium carboxymethyl cellulose, polyvinyl pyrrolidone or maleic anhydride/vinyl methyl ether copolymers; hydrotrozolo dyes; fragrances; alkaline substances such as silicates: fluorescent whitening agents: bactericidal agents; anti-fogging agents - suds enhancers: suds suppressants such as liquid polysiloxane anti-foaming compounds: enzymes, especially the commercially available subtilisin MaXatase (G15t-'
Brocades N, V, , Delft, T
from heNetherlands), Alcalase
■ and F&gperase■ (both Novo
Industry' A/S.

Proteolytic, amylolytic and fibrinolytic enzymes such as (from Copenhagen, Denmark):
Enzyme stabilizing systems such as mixtures with polyol/Ji metal borates; diberinphthalic anhydride with or without bleaching precursors such as sodium perborate or sodium percarbonate, tetraacetyl ethylene diamine; or chlorine-free bleaches such as dichlorocyanurate; antioxidants such as sodium sulfite; opacifiers; fabric softeners; stabilizers such as polysaccharide hydrocolloids, e.g. Acetylated xanthan rubber, [Kelzan J (Kel
coComp, .

Buffers and the like.

The invention is further illustrated by the following examples, in which parts and percentages are by weight unless otherwise indicated.

Example I The following composition was made; Ingredients 2% Sodium Dodecyl Penvin Sulfonate 5.07 moles alkylene oxide (92:8 ethylene oxide and propylene oxide)
2.0 Anhydrous sodium tripolyphosphate 21.0 Amorphous silica (particle size 10 nm).

Surface area 700m2/9)
3.0 Sodium Carboxymethyl Cellulose
0.2 Foam inhibitor
0.6 Fluorescent brightener 0
．． 1 Stabilizer D・2 Proteolytic enzyme 8 Enzyme stabilizer 1.0.0 Fragrance 0.25 Water
One left
The final product of the 8.08 enzyme has proteolytic activity of 9 GU, M' (733 GU
/W = 1 Anson unit/9).

In order to demonstrate the anti-corrosion effect of the composition of the present invention, comparative tests were conducted on the composition under various temperature conditions and water hardness levels.

Al-Corrosion Test To evaluate the corrosive effect of the test cleaning fluid, 40crrL
Pure aluminum (99,5% Ai) with a surface area of 2
The disc was cleaned to remove dust and contamination from the surface. It was rinsed with distilled water, soaked in methanol and air dried. After weighing the plates, they were treated with the test solution for 8 hours, during which time the solution was constantly stirred.

The plate was then washed, dried and weighed. The corrosive action of the test liquid was expressed as the weight loss of M per hour and per m2. In all tests, liquid cleaning compositions were added to provide a concentration of 109/cm of cleaning solution, unless otherwise specified.

Corrosion vs. Water Hardness Test The composition of Example I was tested with a control composition (i.e., the example composition containing no silica) and water of various hardness at a temperature of 85° C. according to the method of corrosion testing described above. compared. Water hardness was expressed in degrees of French hardness (1 degree of French hardness is equal to 10 Ya CaCO3/vert).

The following results were obtained: Weight loss of M (&/m, 2/h 0 1 4.0
12.5 1 2
．． 425 <[1,11,13
7,510,4 501<0.1 The composition of Example 1 was compared with the control composition according to the corrosion test method described above at various temperatures using deionized water as the cleaning fluid.

The following results were obtained: Weight loss of M (9/m”/hr) 30 1 0.4 40 1 0.8 50 <0.1 1.26Q
1 1.870 1
2.8 85 1 4.0 These results clearly demonstrate the corrosion inhibiting effect of silica.

Example ■ The following composition was made: Ingredients - % Sodium Dodecyl Benzene Sulfonate 7,0
C1 condensed with 7 moles of alkylene oxide (a mixture of ethylene oxide and propylene oxide in a weight ratio of 92-28)
3- C10 linear primary alcohol 2
．． 0 Coconut Potassium Soap 1.0 Sodium Tripolyphosphate 2
3.8 Amorphous silica (particle size 10 nm.

Surface area)OOm”/9)
2.0 Enzyme stabilizer 7.
0 proteolytic enzyme 9()U7■
Sodium carboxymethyl cellulose
0.1 Fluorescent brightener 0.1 Foam suppressant 0.2 Fragrance
0.6 water
Remaining PH7,
8. In order to illustrate the corrosion effect as a function of product dosage (and thus as a function of silica concentration), the composition of Example 1 was subjected to a corrosion test and tested at a temperature of 85° C. with different product dosages from the control composition. A comparison was made using deionized water as the cleaning solution.

The following results were obtained: Product dosage Silica M weight loss (9/m27
time) 10 200 <0.1
4.09 180 <0.1
4.08 160 <01. 3
．． 97 140 0.5
3.86 120 0.8
3.8 These results clearly show that effective corrosion protection is provided if the product dosage is greater than 69 parts per cubic centimeter, corresponding to 120 ppm by weight of silica.

Example ■ The following composition was made: Sodium dodecylbenzene sulfonate
8.0 sodium laolyl ether sulfate C12- condensed with 0.58 moles of ethylene oxide
Bilinear primary alcohol
2.5.Sodium pyrophosphate
11.0 Amorphous silica (particle size 1
'Onm.

Surface area 700 m2/9)
7.5 Enzyme stabilizer 10
．． 0 proteolytic enzyme 9C) U/
Fluorescent brightener 0.2 water
Remaining FJ (8
,0 The above composition was subjected to the same experiment as that carried out in Example (2). The investigated ranges of product dosages are different since the above products must be used in lower dosages.

The following results were obtained; Product dosage Silica M weight loss (9/m”/
time) 3.0 225 <O,,11,72,
5188<0.1 1.52.0
150 0.4 1.31
．． 5 113 0.7
1.1 At least 120 ppm and preferably 150 ppm in the cleaning solution to provide effective corrosion protection
The above test shows that m silica should be present.

EXAMPLE ■ Corrosion testing was conducted on a set of compositions made according to the formulation of Example H, varying the type of silica used to illustrate the anti-corrosion effects of various types of silica. The amount of silica incorporated was equal to 10% by weight of the composition.

The following results were obtained at 85° C., water hardness of 0° and a product dosage during cleaning of 10 g/vert.

Silica type Elementary particle size Surface area Weight loss of M Durosi11) Precipitated 25 5
0 3. INeosylET” precipitated
30 250 0.1 Tixosi13) 'or'20 250 0.038A GasilWPl') Human o'r"# 1.52.
0 850 0.0Cab-0-8il Thermal M method 14 200 0. [)MB2) Aerosil pyrolysis method 7 380 0
．． 0380"Ga511352)-+-(=or 3-5 300
0.0Gas i 12002) Xerogel
1.5-2.0 700 0.01) Degu
ssa, Germany 2) Crosf
ield, UK 3) BI France 4) Cabot Corp, Ill, USA
Than.

Example■ It was included in an amount of

Dosage during washing 12g/vert, water hardness of Do and procedural amendment (method) 1. Indication of the case Showa J and Nenji I "Publication No. ρ-/pul 1 No. 2, Name of the invention Relationship with the case 1. 'I applicant's address 4, subject of amendment by agent B full-, j) t)', 7+;li, (circle γ substitution) 8, content of amendment

Claims (9)

[Claims] (1) In an aqueous liquid detergent composition with improved non-corrosive properties containing customary detergent ingredients, 200 m2/
A detergent composition further comprising an effective amount of silica having a surface area greater than 9. (2) Silica is included in an amount such that at a suitable washing dosage of all detergent products, a dissolved silica concentration of at least 120 ppm by weight is established in the washing liquid. ) The detergent composition described in item 1. (3) Silica is included in an amount of about 1 to 10% by weight of the total composition (
1) The detergent composition according to item (2). (4) Claim No. (1) = (3) characterized in that the silica has a particle size smaller than 30 nm.
) The detergent composition according to item 1. (5) Claim (1) characterized in that the silica has a surface area greater than 500 m2/9.
- The detergent composition according to any one of item (4). (6) 7 Lika is included in an amount of from 2 to 4% by weight of the total composition (IJ-
(5) The method described in any one of paragraphs. (7) Claim No. (1)-(
The detergent composition according to item 1 of item 6). (8) from 5 to 25% by weight of detergent active materials of anionic, nonionic, cationic and/or zwitterionic type;
Claim 1 - characterized in that in a composition comprising from 5 to 50% by weight of builder material, silica is included in an amount of from 2 to 4% by weight of the total composition.
(The detergent composition according to any one of Item 71. (9) Claims (1) to (8) in the cleaning process
A method for preventing corrosion of mechanical parts during cleaning, characterized in that a composition according to any one of paragraphs 1 to 1 is applied.