CA2034835A1 - Detergent - Google Patents
DetergentInfo
- Publication number
- CA2034835A1 CA2034835A1 CA002034835A CA2034835A CA2034835A1 CA 2034835 A1 CA2034835 A1 CA 2034835A1 CA 002034835 A CA002034835 A CA 002034835A CA 2034835 A CA2034835 A CA 2034835A CA 2034835 A1 CA2034835 A1 CA 2034835A1
- Authority
- CA
- Canada
- Prior art keywords
- weight
- water
- detergent
- sodium disilicate
- amorphous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/08—Silicates
Abstract
Detergent Abstract of the disclosure A detergent containing 5 to 50 % by weight of at least one surfactant, 0.5 to 60% by weight of a matrix sub-stance and also standard laundry aids, contains as matrix substance an amorphous, low-water sodium disilicate having a water content of 0.3 to 6 % by weight which has preferably been produced by partial dehydration of commercially available powdered amorphous sodium disili-cate having a water content of 15 to 23 % by weight.
Description
~ ~ ~0/H 007 The invention relates to a detergent containing 5 to 50 %
by weight, preferably 10 to 30 % by weight, of at least one surfactant, 0.5 to 60 % by weight of a matrix sub-stance and also standard laundry aids.
It has been the prior art for more than 80 years to incorporate sodium silicates, generally in the form of their aqueous solution and also described as waterglass, in detergent formulations.
Sodium silicates were used for a long time, especially in conjunction with soda, ~s matrix substances in deter-gents, but in the course of modern detergent development they were replaced by substances with better builder properties such as, for example, condensed phosphates.
Owing to the restrictive detergent phosphate legislation which ha~ come into force in many European countries and the USA, zeolite 4A in con~unction with polycarboxylates is today the basic matrix substance fo~ many detergent products. The addition of amorphous sodium disilicate in the form of waterglass or as a powder in an amount of around 5 % by weight is also today still usual in the majority of finished detergents. The function of the sodium disilicate is not limited in this connection to its ~orrosion-inhibiting action. It also acts as matrix substance with good absorption properties for liquid constituents and, because of its dispersant action, improves the soil antiredeposition capability of the washing liquor. In addition, it binds some of the harden-ing constituents of the washing water and as a result also benefits the washing result.
As has now been found, surprisingly, the technical washing properties of commercially available sodium disilicates, which normally have a water content of 15 -23 ~ by weight, can be substantially increased if these . - 2 ~ 2~3~
product~ are partially dehydrated.
In order to partially dehydrata such sodium disilicates to form amorphous sodium disilicates having a water content of 0.3 to 6 % by weight, preferably of 0.5 to 2 ~
by weight, for example, the powdered amorphous sodium disilicate having a water content of 15 to 23 % by weight is introduced into a rotary tubular kiln which is arranged at an angle and fitted with devices for agitat-ing solid and in which it is treated in countercurrent with furnace gas at temperatures of 250 to 500C for 1 to 60 minute~, the rotary tubular kiln being insulated in a manner such that the temperature of its outside wall is less than 60C. The amorphous sodium disilicate emerging from the rotary tubular kiln can be comminuted to par-ticle sizes of 0.1 to 12 mm with the aid of a mechanical crusher. Preferably, the comminuted sodium disilicate is ground to a particle size of 2 to 400 ~m in a mill, the mill being operated with a circumferential velocity of 0.5 to 60 m/s.
In detail, the detergent of the pre~e~t invention now comprises an amorphous low-water sodium silicate having a water content ofØ3 to 6 % by weight as matrix sub-stance.
In addition, the detergent of the invention is optionally and preferably one wherein a) the amorphous sodium disilicat.e contains 0.5 to 2 %
by weight of water;
b) the amorphous low-water sodium disilicate it con-: tains as matrix substance has been produced by : 30 partial.- dehydration-.-.of ~ co .. ercially available powdered amorphous sodium disilicate havin~ a water ccntent of 15 to 23 % by weight c) the amorphous low-water sodium disilicate it con-tains as matrix substance has been produced by introducing powdered amorphous sodium disilicate having a water content of 15 to 23 % by weiyht into . . .
;
2Q3~?5 a rotary tubular kiln arranged at an angle and fitted with devices for agitating solid and in which it has been treated in countercurrent with furnace gas at temperatures of 250 to 500C for 1 to 60 minutes, the tubular rotary kiln having been insu-lated in a manner such that the temperature of its outside wall was less than 60C, and by comminuting the amorphous sodium disilicate emerging from the rotary tubular kiln to a particle size of 0.1 to 12 mm with the aid of a mechanical crusher and then grinding to a particle size of 2 to 400 ~m with a mill.
Starting from a commercially available sodium disilicate having a water content of 18 % by weight, the following partially dehydrated products were produced:
Example Water content (% by weight of H2O) I (starting material) 18 II ,0.3 III 0.7 IV 1.5 .. V 3.1 Vl 5 ~ Detergents were manufactured by the spray mist mixing : process in accordance with the following basic formula-tion containing the individual sodium disilicate species (NaDS; Examples I - VI) .
;
~ 4 ~ 2~
Detergent f~ ,rmulations % by weight Constituents A B
~w~ _ NaDS . aq (Example I-VI) 25 ) Na perborate tetrahydrate 10.0 10.0 Na percarbonate 8.0 8.0 Anionic surfactants 12.0 12.0 alkyl benzenesulfonate 7.5 7.5 soap 4.5 4.5 Nonionic surfactants 5.0 5.0 Ifatty alcohol ethoxylate~) . Polycarboxylate (acrylic 4.9 400 acid/maleic acid, MM approx. 60,0000) Cellulose ether 2.0 2.0 Enzymes O.5 O.5 Optical brighteners 0.2 0.2 Na sulfate, water and to 100 to 100 minor constituents .
) in all cases calculated for Na2Si205 ln all cases 2.5 g or 4.5 g of the Na disilicates in accordan~e with Examples I - VI were dissolved in lOOOml of water of 18 German hardness for the purpose of determining their water hardness bonding capacity (remaining residual water hardness), the ~olution was stirred for exactly 1/2 hour at 60C by means of a magnetic stirrer at approximately 500 rev/min, then cooled rapidly to 20C in ic~ water and qubsequently freed from insoluble residue by means of-a membrane filter having a pore size of 0.45 ~m. The ~ame procedure was also carried out with the water used of 18 German hardness not containing added Na disilicate in order to eliminate the error which could arise through a possible precipitation of Ca and Ng as carbonate.
- 5 ~ 2 ~3 ~ ~ 3 ~
In the same way 10 g of the detergents based on the above basic formulation containing Na disilicate in accordance with Examples I - VI were dissolved in each case in watsr of 18 German hardness and the solutions were treated as S described above. The basic formulation not containing added Na disilicate was used as a blank sample in the experimental series.
The residual contents of calcium and magnesium, which are listed in Table 1, in the filtrates of the individual solutions and also in the identically treated and fil-tered water without additive were determined by means of atomic absorption:
~ . .
- 6 - ~?~?~
_ , ._. j. ,~ :
~o O ~
~, o O ~ s~ 5s S t~s ,_, ~,, .
~ o~ S In ~ u~
O N O . . ~
¦ O
a ~0; ~ c~ 1 . N ~S L~
a s~ o ~w c~l s~ ~ N S.~ ~s !n ~ .3 ~ ~ ~s ~ t . . .1 .~ I r m I ~ . c~ cn n l _ .1 ~ - I~ s In c~ 'rs , ~, ) ~ sn n ~ ~ C~lC,S ~1 _ l ~ ` `' S i ._ N C~ J N N _ : : .
~: - ae X x ~ e ~
i ct~ o o .~ ~In . o U~ In ~ ~ tn In ~ ~ :
~: ~t O O OO OO ~ P ~ 1 L. X I Z Z Z Z Z Z i~
-:
by weight, preferably 10 to 30 % by weight, of at least one surfactant, 0.5 to 60 % by weight of a matrix sub-stance and also standard laundry aids.
It has been the prior art for more than 80 years to incorporate sodium silicates, generally in the form of their aqueous solution and also described as waterglass, in detergent formulations.
Sodium silicates were used for a long time, especially in conjunction with soda, ~s matrix substances in deter-gents, but in the course of modern detergent development they were replaced by substances with better builder properties such as, for example, condensed phosphates.
Owing to the restrictive detergent phosphate legislation which ha~ come into force in many European countries and the USA, zeolite 4A in con~unction with polycarboxylates is today the basic matrix substance fo~ many detergent products. The addition of amorphous sodium disilicate in the form of waterglass or as a powder in an amount of around 5 % by weight is also today still usual in the majority of finished detergents. The function of the sodium disilicate is not limited in this connection to its ~orrosion-inhibiting action. It also acts as matrix substance with good absorption properties for liquid constituents and, because of its dispersant action, improves the soil antiredeposition capability of the washing liquor. In addition, it binds some of the harden-ing constituents of the washing water and as a result also benefits the washing result.
As has now been found, surprisingly, the technical washing properties of commercially available sodium disilicates, which normally have a water content of 15 -23 ~ by weight, can be substantially increased if these . - 2 ~ 2~3~
product~ are partially dehydrated.
In order to partially dehydrata such sodium disilicates to form amorphous sodium disilicates having a water content of 0.3 to 6 % by weight, preferably of 0.5 to 2 ~
by weight, for example, the powdered amorphous sodium disilicate having a water content of 15 to 23 % by weight is introduced into a rotary tubular kiln which is arranged at an angle and fitted with devices for agitat-ing solid and in which it is treated in countercurrent with furnace gas at temperatures of 250 to 500C for 1 to 60 minute~, the rotary tubular kiln being insulated in a manner such that the temperature of its outside wall is less than 60C. The amorphous sodium disilicate emerging from the rotary tubular kiln can be comminuted to par-ticle sizes of 0.1 to 12 mm with the aid of a mechanical crusher. Preferably, the comminuted sodium disilicate is ground to a particle size of 2 to 400 ~m in a mill, the mill being operated with a circumferential velocity of 0.5 to 60 m/s.
In detail, the detergent of the pre~e~t invention now comprises an amorphous low-water sodium silicate having a water content ofØ3 to 6 % by weight as matrix sub-stance.
In addition, the detergent of the invention is optionally and preferably one wherein a) the amorphous sodium disilicat.e contains 0.5 to 2 %
by weight of water;
b) the amorphous low-water sodium disilicate it con-: tains as matrix substance has been produced by : 30 partial.- dehydration-.-.of ~ co .. ercially available powdered amorphous sodium disilicate havin~ a water ccntent of 15 to 23 % by weight c) the amorphous low-water sodium disilicate it con-tains as matrix substance has been produced by introducing powdered amorphous sodium disilicate having a water content of 15 to 23 % by weiyht into . . .
;
2Q3~?5 a rotary tubular kiln arranged at an angle and fitted with devices for agitating solid and in which it has been treated in countercurrent with furnace gas at temperatures of 250 to 500C for 1 to 60 minutes, the tubular rotary kiln having been insu-lated in a manner such that the temperature of its outside wall was less than 60C, and by comminuting the amorphous sodium disilicate emerging from the rotary tubular kiln to a particle size of 0.1 to 12 mm with the aid of a mechanical crusher and then grinding to a particle size of 2 to 400 ~m with a mill.
Starting from a commercially available sodium disilicate having a water content of 18 % by weight, the following partially dehydrated products were produced:
Example Water content (% by weight of H2O) I (starting material) 18 II ,0.3 III 0.7 IV 1.5 .. V 3.1 Vl 5 ~ Detergents were manufactured by the spray mist mixing : process in accordance with the following basic formula-tion containing the individual sodium disilicate species (NaDS; Examples I - VI) .
;
~ 4 ~ 2~
Detergent f~ ,rmulations % by weight Constituents A B
~w~ _ NaDS . aq (Example I-VI) 25 ) Na perborate tetrahydrate 10.0 10.0 Na percarbonate 8.0 8.0 Anionic surfactants 12.0 12.0 alkyl benzenesulfonate 7.5 7.5 soap 4.5 4.5 Nonionic surfactants 5.0 5.0 Ifatty alcohol ethoxylate~) . Polycarboxylate (acrylic 4.9 400 acid/maleic acid, MM approx. 60,0000) Cellulose ether 2.0 2.0 Enzymes O.5 O.5 Optical brighteners 0.2 0.2 Na sulfate, water and to 100 to 100 minor constituents .
) in all cases calculated for Na2Si205 ln all cases 2.5 g or 4.5 g of the Na disilicates in accordan~e with Examples I - VI were dissolved in lOOOml of water of 18 German hardness for the purpose of determining their water hardness bonding capacity (remaining residual water hardness), the ~olution was stirred for exactly 1/2 hour at 60C by means of a magnetic stirrer at approximately 500 rev/min, then cooled rapidly to 20C in ic~ water and qubsequently freed from insoluble residue by means of-a membrane filter having a pore size of 0.45 ~m. The ~ame procedure was also carried out with the water used of 18 German hardness not containing added Na disilicate in order to eliminate the error which could arise through a possible precipitation of Ca and Ng as carbonate.
- 5 ~ 2 ~3 ~ ~ 3 ~
In the same way 10 g of the detergents based on the above basic formulation containing Na disilicate in accordance with Examples I - VI were dissolved in each case in watsr of 18 German hardness and the solutions were treated as S described above. The basic formulation not containing added Na disilicate was used as a blank sample in the experimental series.
The residual contents of calcium and magnesium, which are listed in Table 1, in the filtrates of the individual solutions and also in the identically treated and fil-tered water without additive were determined by means of atomic absorption:
~ . .
- 6 - ~?~?~
_ , ._. j. ,~ :
~o O ~
~, o O ~ s~ 5s S t~s ,_, ~,, .
~ o~ S In ~ u~
O N O . . ~
¦ O
a ~0; ~ c~ 1 . N ~S L~
a s~ o ~w c~l s~ ~ N S.~ ~s !n ~ .3 ~ ~ ~s ~ t . . .1 .~ I r m I ~ . c~ cn n l _ .1 ~ - I~ s In c~ 'rs , ~, ) ~ sn n ~ ~ C~lC,S ~1 _ l ~ ` `' S i ._ N C~ J N N _ : : .
~: - ae X x ~ e ~
i ct~ o o .~ ~In . o U~ In ~ ~ tn In ~ ~ :
~: ~t O O OO OO ~ P ~ 1 L. X I Z Z Z Z Z Z i~
-:
2 ~
From the values found for the residual water hardness, the superiority of the partially dehydrated Na disili-cates (Examples II - VI) over the starting products containing 18 % by weight of HzO (Example I) emerges clearly.
Since a higher capacity to bond the water hardness in general also makes it possible to expect an improvement in the washing result, washing experiments were carried out in a domestic washing machine under the following conditions using the detergents (type A) which had been finished with the individual Na disilicate species in accordance with Examples I - IV:
Washing machine: Miele TMT
Temperature: 60C
Water hardness: 18 German hardness Ballast: 3.75 kg of unsoiled test fabric Program: one-wash cycle Detergent dosage: 175 g Test fabric used: 0 (EMPA = Swiss Naterial Testing Institute, St. Gallen, Switzerland;
WFR = Laundry Research, Rrefeld) a) For primary washing effect (30il removal and bleach-ing) ENPA BW 101 (standard ~oiling) EMPA PE/BW 104 (standard soiling) WFR BW lOC (standard soiling) WF~ BW lOG (tea soiling) WFR PE/BW 20G (tea soiling) 0 b) for secondary wa~hing effect:
EMPA - cotton WFR - terry cloth The primary washing effect was tested by means of optical remission measurement and expressed in the form of the remission difference which is obtained from the dif-ference in the values after and before washing:
~R = Ra - F~
~R = remission difference (%) Ra = remission after washing (~) Rb = remission before washing (%) The ash value as a measure of the fabric incrustation was determined after 25 laundering cycles by determining the ignition residue in percent at 800C.
Table 2 summarizes the washing results which were obtained with the detergents (type A) based on ~a disili-cates in accordance with Examples I - VI. As expected, the detergents (type A) finished with partially dehyd-rated Na disilicate exhibit a marked superiority over the detergent formulation based on the starting product (Example I, Na disilicate containing 18 % H2O).
The detergents (type A) produced on the basi3 of Examples I - VI were sub~ected to a test to determine shelf life.
In this, the individual detergent samples were stored in sealed pasteboard boxes7 (wax box, water vapor perme-ability: approximately 10 g m~2 day~1 in a climatic test chamber at 37C and 70 % relative atmospheric humidity for 4 weeks. The flowability was determined in accordance with Table 3. As can be gathered from Table 3, the detergents (type A) based on the partially dehydrated products according to the invention (Examples II - VI) appear clearly^superior in that they more or less retain their flowability while the commercially available Na disilicate (Example I) hardens completely under the chosen storage conditions.
.
~3~
_ _ N O _ .
. _ C`~ O ~1 Cl. . .. ___ 1 ~ '~0 , ~ ~ ~ i~ ' ~b -- m , N N N ~ ~ U ~ j ,~
_ _ ~ ~rC
~ i ~ ~ o 2 N N C~ l ~ i~
l ,'~ - '~o _ ,C~.. c t~ I~.O . O N N C~J jNN C~l ~Odp O
W Up~ ~ _ ~ O ~ C 0, ~ ,~ ~ olU~ ~
E~ ~ o ~ql.¢
~ ~~ . ~
o ~ ~~ ~ .
~ q _ _ a ~ ~.~ ~ . a) ~ G~ -oN ~ o . .C ~ ' ~ O O O O O ~ ~ O O O O O
~ jC ~ ~ T T S S S p~_~ T T S S S
1~ ' ~ ,~ -01 ~
~11~ _ O, .~_ O.
8 ~ 8 c~ 8 ~a ~ c c:
,, ~'c z z z z z ~uZ z z z'z _ _ = 3 ~ ~ 5 . . .
11 2~3~5 Anionic surfactants are understood to mean the water-soluble salts of higher fatty acids or resin acids such as sodium soaps or potassium soaps of coconut, palm kernel or rape oil and also of tallow and mixtures thereof. They furthermore include higher alkyl-substituted aromatic sulfonates such as alkylbenzenesul-fonates containing 9 to 14 carbon atoms in the alkyl radical, alkylnaphthalenesulfonates, alkyltoluenesul-fonates, alkylxylenesulfonates or alkylphenolsulfonates;
fatty alcohol sulfates (R-CH2-O-S03Na; R = C1l17) or fatty alcohol ether sulfates such as alkali-metal lauryl sulfate or alkali-metal hexadecyl sulfate, triethanol-amine lauryl sulfate, sodium oleyl sulfate or potassium oleyl sulfate, sodium salts or potassium salts of lauryl sulfate ethoxylated with 2 to 6 mol of ethylene oxide.
Further suitable anionic surfactants are secondary linear alkanesulfonates such as ~-olefinsulfonates having a chain length of 12-20 carbon atoms.
Nonionic surfactants are under~tood to mean those com-pounds which contain an organic hydrophobic group andalso a hydrophilic radical, for example ~he condensation products of alkylphenols or higher fatty alcohols with ethylene oxide (fatty alcohol ethoxylates), the conden-sation products of polypropylene glycol with ethylene oxide or propylene oxide, the condensation products of ethylene oxide with~reaction product. of ethylenediamine and propylene oxide and also long-chain tertiary amine oxides ( Cl H3 Finally surfactants having zwitterionic (ampholytic) character comprise the following compounds:
Derivatives of aliphatic secondary and tertiary amines or quaternary ammonium compounds containing 8 to 18 carbon atoms and a hydrophilic group in the aliphatic radical such as, for example, sodium 3-dodecylaminopropionate, 2 ~ Q 3 i ~ ~
sodium 3-dodecylaminopropanesulf~, 3-tN,N-dimethyl-N-hexadecylamino)propane-l-sulfonate or fatty acid amino-alkyl-N,N-dimethylacetobetaine, the fatty acid containing 8 to 18 carbon atoms and the alkyl radical 1 - 3 carbon atoms.
Suitable laundry aids according to the invention are inorganic or organic salts, in particular inorganic or organic complexing agents, having a weakly acid, neutral or alkaline reaction.
Usable salts with a weakly acid, neutral or alkaline reaction are, for example, the bicarbona~es or carbonates of the alkali metals, furthermore the alkali-metal salts of organic non-capillary-active sulfonic acids containing 1 to 8 carbon atoms, carboxylic acids and sulfocarboxylic acids. These include, for example, water-soluble salts of benzene-, toluene- or xylenesulfonic acid, water-soluble salts of ~ulfoacetic acid, sulfobenzoic acid or salts of sulfodicarboxylic acids and also the salts of acetic acid, lactic acid, citric acid, tartaric acid, oxy-diacetic acid (HOOC-CH2-0-CH2-COOH), oxydisuccinic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, polycarboxy-lates, polyacrylic acid and polymaleic acid. The organic complexing agents include, for example, nitrilotriacetic acid, ethylenediaminetetraacetic acid, N-hydroxyethyl-ethylenediaminetriacetic acid or polyalkylene-polyamine-N-polycarboxylic acids.
Laundry aids according to the invention furthermore comprise products such as the alkali-metal salts or Immonium salts of sulfuric acid, boric acid, alkylene-, p 30 hydroxyalkylene- or aminoalkylenephosphonic acid and also bleaching agents, stabilizers for peroxide compounds (bleaching agents) and water-soluble organic complexing agents.
. ~ .
In detail, the bleaching agents include sodium perborate mono- or tetrahydrate, Na percarbonate, the alkali-metal . .
'~i - 13 - 2 ~?~2~
salts of perox~mono- or peroxcdisulfuric acid, the alkali-metal salts of perox~diphospho~ic acid (H4P208), and alkali-metal salts of peroxycarboxylic acids such as diperoxydodecanedioic acid. Water-soluble precipitated magnesium silicate, organic complexing agents such as the alkali-metal salts of iminodiacetic acid, nitrilotri-acetic acid, ethylenediaminetetraacetic acid, methylene-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid and nitrilotrismethylenephosphonic acid act as stabil-izers for these bleaches.
Laundry aids which increase the soil antiredepositioncapability of wash liquors, such as carboxymethylcellu-lose, carboxymethyl starch, methylcellulose or copolymers of maleic anhydride with methyl vinyl ether or acrylic acid, foam regulators such as mono- and dialkyl phos-phoric acid esters containing 16 to 20 carbon atoms in the alkyl radical and also optical brighteners, disinfec-tants and enzymes such as proteases, amylases and lip-ases, can also be additional constituents of the deter-gent of the invention.
From the values found for the residual water hardness, the superiority of the partially dehydrated Na disili-cates (Examples II - VI) over the starting products containing 18 % by weight of HzO (Example I) emerges clearly.
Since a higher capacity to bond the water hardness in general also makes it possible to expect an improvement in the washing result, washing experiments were carried out in a domestic washing machine under the following conditions using the detergents (type A) which had been finished with the individual Na disilicate species in accordance with Examples I - IV:
Washing machine: Miele TMT
Temperature: 60C
Water hardness: 18 German hardness Ballast: 3.75 kg of unsoiled test fabric Program: one-wash cycle Detergent dosage: 175 g Test fabric used: 0 (EMPA = Swiss Naterial Testing Institute, St. Gallen, Switzerland;
WFR = Laundry Research, Rrefeld) a) For primary washing effect (30il removal and bleach-ing) ENPA BW 101 (standard ~oiling) EMPA PE/BW 104 (standard soiling) WFR BW lOC (standard soiling) WF~ BW lOG (tea soiling) WFR PE/BW 20G (tea soiling) 0 b) for secondary wa~hing effect:
EMPA - cotton WFR - terry cloth The primary washing effect was tested by means of optical remission measurement and expressed in the form of the remission difference which is obtained from the dif-ference in the values after and before washing:
~R = Ra - F~
~R = remission difference (%) Ra = remission after washing (~) Rb = remission before washing (%) The ash value as a measure of the fabric incrustation was determined after 25 laundering cycles by determining the ignition residue in percent at 800C.
Table 2 summarizes the washing results which were obtained with the detergents (type A) based on ~a disili-cates in accordance with Examples I - VI. As expected, the detergents (type A) finished with partially dehyd-rated Na disilicate exhibit a marked superiority over the detergent formulation based on the starting product (Example I, Na disilicate containing 18 % H2O).
The detergents (type A) produced on the basi3 of Examples I - VI were sub~ected to a test to determine shelf life.
In this, the individual detergent samples were stored in sealed pasteboard boxes7 (wax box, water vapor perme-ability: approximately 10 g m~2 day~1 in a climatic test chamber at 37C and 70 % relative atmospheric humidity for 4 weeks. The flowability was determined in accordance with Table 3. As can be gathered from Table 3, the detergents (type A) based on the partially dehydrated products according to the invention (Examples II - VI) appear clearly^superior in that they more or less retain their flowability while the commercially available Na disilicate (Example I) hardens completely under the chosen storage conditions.
.
~3~
_ _ N O _ .
. _ C`~ O ~1 Cl. . .. ___ 1 ~ '~0 , ~ ~ ~ i~ ' ~b -- m , N N N ~ ~ U ~ j ,~
_ _ ~ ~rC
~ i ~ ~ o 2 N N C~ l ~ i~
l ,'~ - '~o _ ,C~.. c t~ I~.O . O N N C~J jNN C~l ~Odp O
W Up~ ~ _ ~ O ~ C 0, ~ ,~ ~ olU~ ~
E~ ~ o ~ql.¢
~ ~~ . ~
o ~ ~~ ~ .
~ q _ _ a ~ ~.~ ~ . a) ~ G~ -oN ~ o . .C ~ ' ~ O O O O O ~ ~ O O O O O
~ jC ~ ~ T T S S S p~_~ T T S S S
1~ ' ~ ,~ -01 ~
~11~ _ O, .~_ O.
8 ~ 8 c~ 8 ~a ~ c c:
,, ~'c z z z z z ~uZ z z z'z _ _ = 3 ~ ~ 5 . . .
11 2~3~5 Anionic surfactants are understood to mean the water-soluble salts of higher fatty acids or resin acids such as sodium soaps or potassium soaps of coconut, palm kernel or rape oil and also of tallow and mixtures thereof. They furthermore include higher alkyl-substituted aromatic sulfonates such as alkylbenzenesul-fonates containing 9 to 14 carbon atoms in the alkyl radical, alkylnaphthalenesulfonates, alkyltoluenesul-fonates, alkylxylenesulfonates or alkylphenolsulfonates;
fatty alcohol sulfates (R-CH2-O-S03Na; R = C1l17) or fatty alcohol ether sulfates such as alkali-metal lauryl sulfate or alkali-metal hexadecyl sulfate, triethanol-amine lauryl sulfate, sodium oleyl sulfate or potassium oleyl sulfate, sodium salts or potassium salts of lauryl sulfate ethoxylated with 2 to 6 mol of ethylene oxide.
Further suitable anionic surfactants are secondary linear alkanesulfonates such as ~-olefinsulfonates having a chain length of 12-20 carbon atoms.
Nonionic surfactants are under~tood to mean those com-pounds which contain an organic hydrophobic group andalso a hydrophilic radical, for example ~he condensation products of alkylphenols or higher fatty alcohols with ethylene oxide (fatty alcohol ethoxylates), the conden-sation products of polypropylene glycol with ethylene oxide or propylene oxide, the condensation products of ethylene oxide with~reaction product. of ethylenediamine and propylene oxide and also long-chain tertiary amine oxides ( Cl H3 Finally surfactants having zwitterionic (ampholytic) character comprise the following compounds:
Derivatives of aliphatic secondary and tertiary amines or quaternary ammonium compounds containing 8 to 18 carbon atoms and a hydrophilic group in the aliphatic radical such as, for example, sodium 3-dodecylaminopropionate, 2 ~ Q 3 i ~ ~
sodium 3-dodecylaminopropanesulf~, 3-tN,N-dimethyl-N-hexadecylamino)propane-l-sulfonate or fatty acid amino-alkyl-N,N-dimethylacetobetaine, the fatty acid containing 8 to 18 carbon atoms and the alkyl radical 1 - 3 carbon atoms.
Suitable laundry aids according to the invention are inorganic or organic salts, in particular inorganic or organic complexing agents, having a weakly acid, neutral or alkaline reaction.
Usable salts with a weakly acid, neutral or alkaline reaction are, for example, the bicarbona~es or carbonates of the alkali metals, furthermore the alkali-metal salts of organic non-capillary-active sulfonic acids containing 1 to 8 carbon atoms, carboxylic acids and sulfocarboxylic acids. These include, for example, water-soluble salts of benzene-, toluene- or xylenesulfonic acid, water-soluble salts of ~ulfoacetic acid, sulfobenzoic acid or salts of sulfodicarboxylic acids and also the salts of acetic acid, lactic acid, citric acid, tartaric acid, oxy-diacetic acid (HOOC-CH2-0-CH2-COOH), oxydisuccinic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, polycarboxy-lates, polyacrylic acid and polymaleic acid. The organic complexing agents include, for example, nitrilotriacetic acid, ethylenediaminetetraacetic acid, N-hydroxyethyl-ethylenediaminetriacetic acid or polyalkylene-polyamine-N-polycarboxylic acids.
Laundry aids according to the invention furthermore comprise products such as the alkali-metal salts or Immonium salts of sulfuric acid, boric acid, alkylene-, p 30 hydroxyalkylene- or aminoalkylenephosphonic acid and also bleaching agents, stabilizers for peroxide compounds (bleaching agents) and water-soluble organic complexing agents.
. ~ .
In detail, the bleaching agents include sodium perborate mono- or tetrahydrate, Na percarbonate, the alkali-metal . .
'~i - 13 - 2 ~?~2~
salts of perox~mono- or peroxcdisulfuric acid, the alkali-metal salts of perox~diphospho~ic acid (H4P208), and alkali-metal salts of peroxycarboxylic acids such as diperoxydodecanedioic acid. Water-soluble precipitated magnesium silicate, organic complexing agents such as the alkali-metal salts of iminodiacetic acid, nitrilotri-acetic acid, ethylenediaminetetraacetic acid, methylene-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid and nitrilotrismethylenephosphonic acid act as stabil-izers for these bleaches.
Laundry aids which increase the soil antiredepositioncapability of wash liquors, such as carboxymethylcellu-lose, carboxymethyl starch, methylcellulose or copolymers of maleic anhydride with methyl vinyl ether or acrylic acid, foam regulators such as mono- and dialkyl phos-phoric acid esters containing 16 to 20 carbon atoms in the alkyl radical and also optical brighteners, disinfec-tants and enzymes such as proteases, amylases and lip-ases, can also be additional constituents of the deter-gent of the invention.
Claims (4)
1. A detergent which comprises 5 to 50 % by weight of at least one surfactant, 0.5 to 60 % by weight of amorphous low-water sodium disilicate having a water content of 0.3 to 6 % by weight as matrix substance and also standard laundry aids.
2. The detergent as claimed in claim l, wherein the amorphous sodium disilicate contains 0.5 to 2 % by weight of water.
3. The detergent as claimed in claim 1, wherein the amorphous low-water sodium disilicate has been produced by partial dehydration of commercial powdered amorphous sodium disilicate having a water content of 15 to 23 % by weight.
4. The detergent as claimed in claim 3, wherein the amorphous low-water sodium disilicate has been obtained by introducing powdered amorphous sodium disilicate having a water content of 15 to 23 % by weight into a rotary tubular kiln arranged at an angle and fitted with devices for agitating solid and in which it has been treated in countercurrent with furnace gas at temperatures from 250 to 500°C
for 1 to 60 minutes, the rotary tubular kiln having been insulated in a manner such that the temperature of its outside wall was less than 60°C, and by comminuting the amorphous sodium disilicate emerging from the rotary tubular kiln to a particle size of 0.1 to 12 mm with a mechanical crusher and then grinding to a particle size of 2 to 400 µm with a mill.
for 1 to 60 minutes, the rotary tubular kiln having been insulated in a manner such that the temperature of its outside wall was less than 60°C, and by comminuting the amorphous sodium disilicate emerging from the rotary tubular kiln to a particle size of 0.1 to 12 mm with a mechanical crusher and then grinding to a particle size of 2 to 400 µm with a mill.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4004626.5 | 1990-02-15 | ||
| DE4004626A DE4004626A1 (en) | 1990-02-15 | 1990-02-15 | LAUNDRY DETERGENT |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2034835A1 true CA2034835A1 (en) | 1991-08-16 |
Family
ID=6400169
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002034835A Abandoned CA2034835A1 (en) | 1990-02-15 | 1991-01-23 | Detergent |
Country Status (21)
| Country | Link |
|---|---|
| US (1) | US5096609A (en) |
| EP (1) | EP0444415B1 (en) |
| JP (1) | JPH0726290A (en) |
| KR (1) | KR910015694A (en) |
| AR (1) | AR245495A1 (en) |
| AT (1) | ATE122092T1 (en) |
| BR (1) | BR9100594A (en) |
| CA (1) | CA2034835A1 (en) |
| DE (2) | DE4004626A1 (en) |
| DK (1) | DK0444415T3 (en) |
| ES (1) | ES2072456T3 (en) |
| FI (1) | FI97237C (en) |
| HR (1) | HRP921352A2 (en) |
| LT (1) | LTIP1444A (en) |
| LV (1) | LV10482B (en) |
| NO (1) | NO176326C (en) |
| PT (1) | PT96767B (en) |
| RU (1) | RU2024609C1 (en) |
| SI (1) | SI9110269A (en) |
| TR (1) | TR25396A (en) |
| YU (1) | YU26991A (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5433885A (en) * | 1991-07-17 | 1995-07-18 | Church & Dwight Co., Inc. | Stabilization of silicate solutions |
| US5431847A (en) * | 1991-07-17 | 1995-07-11 | Charles B. Barris | Aqueous cleaning concentrates |
| US5261967A (en) * | 1991-07-17 | 1993-11-16 | Church & Dwight Co, Inc. | Powdered electric circuit assembly cleaner |
| US5234505A (en) * | 1991-07-17 | 1993-08-10 | Church & Dwight Co., Inc. | Stabilization of silicate solutions |
| USRE35115E (en) * | 1991-07-17 | 1995-12-12 | Church & Dwight Co. Inc. | Low foaming effective hydrotrope |
| USRE35045E (en) * | 1991-07-17 | 1995-10-03 | Church & Dwight Co., Inc. | Method for removing soldering flux with alkaline metal carbonate salts and an alkali metal silicate |
| US5234506A (en) * | 1991-07-17 | 1993-08-10 | Church & Dwight Co., Inc. | Aqueous electronic circuit assembly cleaner and method |
| US5264046A (en) * | 1991-07-17 | 1993-11-23 | Church & Dwight Co., Inc. | Aqueous electronic circuit assembly cleaner and cleaning method |
| USRE35017E (en) * | 1991-07-17 | 1995-08-15 | Church & Dwight Co., Inc. | Method for removing soldering flux with alkaline salts, an alkali metal silicate and anionic polymer |
| US5264047A (en) * | 1991-07-17 | 1993-11-23 | Church & Dwight Co., Inc. | Low foaming effective hydrotrope |
| EP0639639B2 (en) * | 1993-08-17 | 2010-07-28 | The Procter & Gamble Company | Detergent compositions comprising percarbonate bleaching agents |
| AU685500B2 (en) * | 1993-08-23 | 1998-01-22 | Pq Holding, Inc. | Amorphous alkali metal silicate, process and uses |
| DE4400024A1 (en) * | 1994-01-03 | 1995-07-06 | Henkel Kgaa | Silicate builders and their use in detergents and cleaning agents as well as multi-component mixtures for use in this field |
| DE4406592A1 (en) * | 1994-03-01 | 1995-09-07 | Henkel Kgaa | Improved multi-substance mixtures based on water-soluble alkali silicate compounds and their use, in particular for use as builders in detergents and cleaners |
| DE4415362A1 (en) * | 1994-05-02 | 1995-11-09 | Henkel Kgaa | Process for the production of silicate builder granules with increased bulk density |
| FR2743085B1 (en) * | 1995-12-29 | 1999-02-26 | Rhone Poulenc Chimie | DETERGENT COMPOSITION FOR THE WASHING OF LAUNDRY CONTAINING SODIUM SILICATE AS A MAIN DETERGENCE ADJUVANT |
| US5747439A (en) * | 1996-04-02 | 1998-05-05 | Church & Dwight Co, Inc. | Aqueous sodium salt metal cleaner |
| DE50210858D1 (en) * | 2002-11-02 | 2007-10-18 | Dalli Werke Gmbh & Co Kg | Water-soluble builder of specific particle size in detergents and cleaners |
| DK1416039T3 (en) * | 2002-11-02 | 2008-07-14 | Dalli Werke Gmbh & Co Kg | Use of water-soluble builders with certain grain sizes in detergents without bleach |
| WO2009125335A2 (en) * | 2008-04-07 | 2009-10-15 | Ecolab Inc. | Ultra-concentrated liquid degreaser composition |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1617040A1 (en) * | 1966-03-24 | 1971-02-25 | Renato Dr Altieri | Process for the production of a soap-like, solid detergent obtained by pressing powders |
| US3847663A (en) * | 1970-07-24 | 1974-11-12 | Lubrizol Corp | Cleaning of metals with compositions containing alkali metal silicate and chloride |
| US3816320A (en) * | 1972-11-24 | 1974-06-11 | Fmc Corp | Stable dishwashing compositions containing sodium dichloroisocyanurate dihydrate |
| US4077897A (en) * | 1976-02-13 | 1978-03-07 | The Procter & Gamble Company | Process for preparing detergent compositions |
| CA1102653A (en) * | 1976-03-25 | 1981-06-09 | Tom H. Ohren | Detergent composition |
| IT1160682B (en) * | 1977-10-14 | 1987-03-11 | Po Corp. | DETERGENT COMPOSITIONS WITH SILANO-ZEOLITE ADJUVANT |
| US4199468A (en) * | 1977-11-07 | 1980-04-22 | The Procter & Gamble Company | Alkaline dishwasher detergent |
| US4390441A (en) * | 1980-04-11 | 1983-06-28 | Lever Brothers Company | Machine dishwashing composition |
| US4806260A (en) * | 1986-02-21 | 1989-02-21 | Colgate-Palmolive Company | Built nonaqueous liquid nonionic laundry detergent composition containing acid terminated nonionic surfactant and quarternary ammonium softener and method of use |
| GB8619045D0 (en) * | 1986-08-05 | 1986-09-17 | Ici Plc | Dishwashing compositions |
-
1990
- 1990-02-15 DE DE4004626A patent/DE4004626A1/en not_active Withdrawn
-
1991
- 1991-01-23 ES ES91100795T patent/ES2072456T3/en not_active Expired - Lifetime
- 1991-01-23 DE DE59105345T patent/DE59105345D1/en not_active Expired - Fee Related
- 1991-01-23 CA CA002034835A patent/CA2034835A1/en not_active Abandoned
- 1991-01-23 AT AT91100795T patent/ATE122092T1/en active
- 1991-01-23 DK DK91100795.3T patent/DK0444415T3/en active
- 1991-01-23 EP EP91100795A patent/EP0444415B1/en not_active Expired - Lifetime
- 1991-02-01 US US07/649,451 patent/US5096609A/en not_active Expired - Fee Related
- 1991-02-13 FI FI910712A patent/FI97237C/en active IP Right Grant
- 1991-02-13 AR AR91319052A patent/AR245495A1/en active
- 1991-02-13 TR TR91/0155A patent/TR25396A/en unknown
- 1991-02-13 KR KR1019910002501A patent/KR910015694A/en not_active Application Discontinuation
- 1991-02-14 RU SU914894525A patent/RU2024609C1/en active
- 1991-02-14 BR BR919100594A patent/BR9100594A/en not_active IP Right Cessation
- 1991-02-14 JP JP3021008A patent/JPH0726290A/en active Pending
- 1991-02-14 NO NO910598A patent/NO176326C/en unknown
- 1991-02-14 PT PT96767A patent/PT96767B/en not_active IP Right Cessation
- 1991-02-15 YU YU26991A patent/YU26991A/en unknown
- 1991-02-15 SI SI9110269A patent/SI9110269A/en unknown
-
1992
- 1992-11-25 HR HRP-269/91A patent/HRP921352A2/en not_active Application Discontinuation
-
1993
- 1993-05-04 LV LVP-93-279A patent/LV10482B/en unknown
- 1993-11-05 LT LTIP1444A patent/LTIP1444A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| PT96767A (en) | 1991-11-29 |
| YU26991A (en) | 1995-01-31 |
| KR910015694A (en) | 1991-09-30 |
| HRP921352A2 (en) | 1997-04-30 |
| ES2072456T3 (en) | 1995-07-16 |
| FI910712A (en) | 1991-08-16 |
| NO910598D0 (en) | 1991-02-14 |
| ATE122092T1 (en) | 1995-05-15 |
| FI97237C (en) | 1996-11-11 |
| RU2024609C1 (en) | 1994-12-15 |
| DK0444415T3 (en) | 1995-09-04 |
| EP0444415A1 (en) | 1991-09-04 |
| PT96767B (en) | 1998-07-31 |
| LV10482B (en) | 1996-04-20 |
| JPH0726290A (en) | 1995-01-27 |
| EP0444415B1 (en) | 1995-05-03 |
| DE4004626A1 (en) | 1991-08-22 |
| NO176326B (en) | 1994-12-05 |
| SI9110269A (en) | 1996-12-31 |
| FI910712A0 (en) | 1991-02-13 |
| FI97237B (en) | 1996-07-31 |
| LTIP1444A (en) | 1995-05-25 |
| TR25396A (en) | 1993-03-01 |
| NO910598L (en) | 1991-08-16 |
| US5096609A (en) | 1992-03-17 |
| BR9100594A (en) | 1991-10-29 |
| DE59105345D1 (en) | 1995-06-08 |
| LV10482A (en) | 1995-02-20 |
| AR245495A1 (en) | 1994-01-31 |
| NO176326C (en) | 1995-03-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5096609A (en) | Detergent containing sodium disilicate having a water content of 0.3 to 6% by weight | |
| US5780420A (en) | Silicate-based builders and their use in detergents and multicomponent mixtures for use in this field | |
| US4801396A (en) | Dishwasher detergent paste | |
| US4180485A (en) | Spray-dried detergent compositions | |
| US4274975A (en) | Detergent composition | |
| US4605509A (en) | Detergent compositions containing sodium aluminosilicate builders | |
| US4303556A (en) | Spray-dried detergent compositions | |
| US5078895A (en) | Washing agent with storage-stabilized bleach system | |
| JPS6052194B2 (en) | detergent composition | |
| US4344871A (en) | Spray-dried aluminosilicate detergents containing silicate and metaborate | |
| US4216125A (en) | Detergent compositions with silane-zeolite silicate builder | |
| KR100371760B1 (en) | Washing method and clothing detergent composition | |
| US4885101A (en) | Laundry detergents containing fabric-softening clays between 150 and 2000 microns in size | |
| EP0790298B1 (en) | Washing method and detergent compositions | |
| US4123377A (en) | Particulate detergent composition containing dibasic magnesium hypochlorite | |
| JPH01311197A (en) | Storage stable detergent having enhanced bleaching action | |
| CA1052658A (en) | Method of washing textiles and composition containing inorganic silicates and polycarboxylates and/or polyphosphonates | |
| CA2017958A1 (en) | Builder for textile detergents | |
| US4164478A (en) | Process for improving granular detergents | |
| EP0665815B1 (en) | Amorphous alkali metal silicate, process and uses | |
| US4233173A (en) | Detergent compositions containing dipotassium N-chloroimidodisulfate bleaching agent | |
| GB2063289A (en) | Low phosphate spray-dried powders | |
| DE4418846A1 (en) | Water-sol. amorphous alkali metal silicate modified with organo-silicon gps., | |
| US5232620A (en) | Sodium tripolyphosphate composition and method of producing it | |
| CA1173323A (en) | Agglomeration process for making granular detergents |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |