CA2176336A1 - Additive for use in glass-bottle washing and its use in decreasing glass corrosion - Google Patents
Additive for use in glass-bottle washing and its use in decreasing glass corrosionInfo
- Publication number
- CA2176336A1 CA2176336A1 CA002176336A CA2176336A CA2176336A1 CA 2176336 A1 CA2176336 A1 CA 2176336A1 CA 002176336 A CA002176336 A CA 002176336A CA 2176336 A CA2176336 A CA 2176336A CA 2176336 A1 CA2176336 A1 CA 2176336A1
- Authority
- CA
- Canada
- Prior art keywords
- acid
- additive
- acids
- group
- weight
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/265—Carboxylic acids or salts thereof
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/08—Acids
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3245—Aminoacids
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/36—Organic compounds containing phosphorus
Abstract
The invention concerns an additive for alkaline aqueous washing solutions for use in bottle-washing plants, the additive containing a combination of hydroxyoligocarboxylic acids and phosphonic acids and resulting in a reduction of glass corrosion during washing. The invention also concerns the use of the additive in washing glass-bottles.
Description
~ 1 7~336.~
, , ENGLIS~ TRAN.~.ATTON
OF INTERNATIONAL APPLICATION
An additive for the washing of glass bottle~ and it~ u~
~or reducing gla~s corrosion This invention relates to a new additive for ag,ueous ;llks~l in~ solutions for bottle washing ~-~hinPc for washing glass bottles, more especially beverage bottles.
The function of the additive is to reduce the corrosion 5 of glass which normally occurs under alkaline bottle washing conditions. The invention also relates to the use of the additive in aqueous solutions for the machine washing of glass bottles.
Before reusable beverage bottles of glass are 10 refilled, the labels have to be removed and the bottles thoroughly washed. ~ighly ;~lks~l;nF~ detergent solutions containing sodium hydroxide are normally used for this purpose in the bottle washing machines of bottling fac-tories. The alkali metal hydroxide content is normally in the range from 0 . 5 to 596 by weight and more especially in the range from 1 to 3~6 by weight. Providing suitable products and processes are used, the required cleaning effect is achieved. An unwanted effect in bottle washing is corrosion of the glass. This is a rh~nl nn by which 20 the surface of the glass bottles is chemically attacked, resulting in surface~ roughness. Secondary rhen -n~
often include difficulties in cleaning the rough surface and the danger of microorganism growth in cracks and holes in the surface. It is known from practical experi-25 ence and from laboratory tests that the corrosiveness ofthe cleaning solutions containing sodium hydroxide is increased by an increased percentage content of sodium carbonate .
Since the number of possible rf~f i 11; n~ cycles for 30 reusable glass bottles is limited ~nter alia by the corrosion of glass during the cleaning process, there is ` ~ 2 ~ 7~336 a need for additives which reduce the corrosion of glass in cleaning solutions. Accordingly, the problem ad-dressed by the present invention was to provide a combi-nation of active substances for aqueous Alk~l inP cleaning solutions for the machine washing of glass bottles which, in addition to enhancing the cleaning properties, would contribute towards reducing glass corrosion.
Another problem addressed by the present invention was to formulate this combination of active substances as a concentrate which could be added in situ to the aqueous alkaline cleaning solution.
Aliphatic 11YdLU~Y Ir, lly~lLUXydi- or hydroxytri-carboxlyic acids containing 3 to 6 carbon atoms and l to 5 hydroxy groups are known as ~ onPnts of industrial detergents . It is also known ~hat geminal dirhosrhnn; c acids ~OLL'~ r'~liTl~ to general formula (I) below, amino-methylene ~h~srh~n;c acids corresponding to general for-mula (II) below or rho~rhnnncarboxylic acids c ULLe-~Ulld ing formula (III) below can be added to cleaning solu-tions. It is assumed that the acids mentioned or rather their anions have complexing properties, especially towards the ions r~crnn~:ihle for the hardness of water.
In addition, the rhosrhnn;~ and rho~rhonncarboxylic acids mentioned show so-called scale-inhibiting properties.
DB-C-23 25 829, for example, describes a sequester-ing agent for divalent and trivalent cations in the form of a mixture of l-l~y~lLu~yt:Lhane-~ ;rhosrhnn;c acid, aminotrimethylene rhosrhnn; c acid and 2-rhosrh~nnhutane 1, 2, 4-tricarboxylic acid or water-soluble salts thereof .
This flo~_ I contains details as to which geminal ~;rhncrhnn;C acids, Am;n~ thylene phosphonic acids and rh~srhonc rArboxylic acids may be used as the combination of sequestering agents. The phosphonic acids mentioned in this document, which is hereby included as part of the disclosure of the present invention, are also suitable as ~ ~ 76336 WO 95/13350 3 PCq~/EP94/03618 rhosrhnn;~- acid components for the purposes of the present invention.
The use of hydroxyalkane oligocarboxylic acids as complexing agents in industrial alkaline cleaners is also known. For example, WO 92/0882~ describes a water-containing Alk~linP cleaner for aluminium with a pH value of 10 to 12 which contains an alkaline builder: -nt, Aminn~lkyl or lly~lLuxyclkyl ~l;rht~qrh~ln;c acids, surfac-tants and complexing agents for aluminium. Gluconates and tartrates inter alia are mentioned as complexing agents for aluminium. Hitherto unpublished German patent application P ~2 32 612.5 describes the use of a combina-tion of a rhosrhn~;c acid, an o~;tll~;n~ agent and at least one short-chain organic carboxylic acid selected from inter alia tartaric acid and citric acid in acidic aqueous solutions with a pH value of 0 to 3 for the removal of magnetite coatings in water-carrying systems.
DE:-A-36 03 579 describes acidic cleaning concen-trates containing phosphoric acid in which ethoxylated fatty amines corr~spnnr9in~ to general formula (V) are present as a key constituent:
Rb I
25 R~--N--(CH2--CH2--O) nH (V) In this formula, n is an integer of 2 to 3 0, R" is a linear or branched, saturated or unsaturated alkyl 30 radical containing 8 to 24 carbon atoms and Rl' is a -(CH2-CH2-O)m-H group or a ~ ~ 76336 . .
W0 95/13350 4 PCT/~P94/03618 (CH2-CH~-O) x-H
--R'--N
(CH2-CH2--0) y~H
group, where R~ is an alkylene radical containing 2 to 6 carbon atoms, m, x and y are each numbers of o to 30.
The concentrates also contain a combination of different rhncrhr~nic acids corresponding to general formulae I, II and III below and, in some cases, gluconic acid. The total phosphonic acid content is greater than the gluconic acid content.
German patent application P 43 24 396.7 describes cleaning formulations of high wetting power which are preferably used for cleaning plastic surfaces. They contain as key constituents -- o~mi nn- or diamino or -dicarboxylic acids or amides thereof in combination 20 with relatively long-chain carboxylic acids and nnn;c-nir~
surfactants. These cleaners may contain as optional r-nts llydLu~cyyolycarboxylic acids, such as tartaric acid and citric acid, geminal rl;rhosrhnn;c acids, such as 1 hydL~ ,cy~Lhane-1,1-(l;rhnc:rhnn;c acid, ~m;norhnsrhonic 25 acids and phosrh- nnpolycarboxylic acids. These cleaners may also contain alkali metal hydroxides as builders.
It has surprisingly been found a combination of llydLu~Ly~ligocarboxylic acids and rhosrhnn; c acids known as sequestrants in certain quantity ratios distinctly 30 reduces the corrosion of glass caused by ~lk~l;n~ carbon-ate-containing cleaning solutions. The well-known complexing properties of these active substances had actually been expected to increase the corrosion rate.
In a first .omho~ L, the present invention relates 35 to an additive in the form of an aqueous solution for addition to i~lk~ nF~ cleaning baths for the machine . .. 21 76336 . , washing of glass bottles, consisting of a~ 7 to 25$ by weight, based on the free acid, of one or more aliphatic hydLuxy n~ ydLuxydi- or llydLu~syl-Licar~oxylic acids containing 2 to 6 carbon atoms and 1 to 5 hydroxy groups and/or aliphatic r nAminn- or diamino-mono- or -dicarboxylic acids containing 2 to 6 carbon atoms or water-soluble salts thereof, 10 b) 1 to 12% by weight, based on the free acid, of one or more geminal rl;crhnsrhnn;~ acids corrPcro~ n~ to general formula (I~:
O R O
5HO -- P -- C -- P -- OH ( I ) l l l OH Z OH
in which R is an alkyl radical containing 1 to 5 carbon atoms and Z is 5lydLvg~5l~ a hydroxy group or an amino group, and/or one or more Am;r thylene rh~Erhnn;~ acids c,LL~ L,~ 7;n~J to general formula (II):
Rl - CXY
N -- CXY - R3 ( II ) 3 0 R2 _ CXY
in which X and Y ; n~rPn~lPntly of one another represent hydrogen or an alkyl group containing 1 to 4 carbon atoms, Rl and R2 represent -PO~H2 or a group u uLLt~ ullding to 2 t 76336 the formula H203P - CH2 H203P - CH~
and R3 representS -PO3H2 and/or one or more phosphonocarboxylic acids corre-sponding to general formula (III):
R' I
H203P -- C - COOH (III) I
in which R' is hydrogen, an alkyl group containing 1 to 4 carbon atoms or a -CH2-CH2-COOH group, or water-soluble salts thereof, c) 63 to 92~6 by weight of water or an aqueous 601ution of other ~IlYil;~ries~
the total concentration of the ~arboxylic acids of group a) being no lower than the total .;ul-c~ Lc-tion of the 25 rhrsrhnnic acids of group b).
The additive preferably contains 10 to 20~6 by weight, based on the free aci~, of one or more of the carboxylic acids of group a) or water-soluble salts thereof and/or, preferably and, 2 to 6% by weight, based 30 on the free acid, of one or more of the rhoqrhon;~ acids of group b) or water-soluble salts thereof and 68 to 91%
by weight and preferably 74 to ~38% by weight of water or an a~ueous solution of other auxiliaries.
Since the additive is intended for addition to an 35 llk~l ;n~ cleaning solution, the acids suitable for use in accordance with the invention are present in the in-use solution in the form of their anions irrespective of ` 2~ 76336 . .
whether the additive contains them as free acids or as water-soluble salts. I~ the carboxylic acids of group a) and/or the rhosrhnn; c acids of group b) are used as water-soluble salts, the alkali metal or ammonium salts 5 are particularly suitable, sodium salts preferably being used. The expression "water-soluble" in this regard means that the salts are soluble in the aqueous phase of the additive in the concentration ranges mentioned above, based on the free acids.
Suitable lly~Lu.cy-~.rboxylic acids of group a) are, in particular, hydroxyacetic acid, lactic acid, gluconic acid, tartronic acid, malic acid, tartaric acid and citric acid. Aminocarboxylic acids of group a) are also suitable for the purposes of the invention. The natu-15 rally occurring alpha-amino acids or amino acid deriva-tives are generally chiral in relation to the carbon atom carrying the amino group and are present in the L-form.
Although the chiral L-amino acids do not afford any particular advantages for the t~-hnic~l application 20 according to the invention, they are preferably used as natural active substances or as active substances identi-cal with those occurring in nature. Accordingly, the following amino acids, for example, may be used in the form of their racemates or in optically active form:
25 glycine, alanine, valine, leucine, isoleucine, beta-alanine, gamma-aminobutyric acid, epsilon-aminocaproic acid, glutamine, glutamic acid, aspartic acid, amino-malonic acid, ~m~no~lipic acid and 2-amino-2-methylpen-tanedioic acid. The amino acids may additionally bear 30 hydroxyl groups. Examples of corr~spnr~linq amino acid6 are serine and threonine.
In one particularly advantageous - 'i- 1, the additive contains 2 to 4 and preferably 3 different carboxylic acids, more esp~ lly ~ly.lL~Ly-cLrboxylic acids 35 of group a), the combination of gluconic acid, lactic acid and citric acid leading to particularly positive results. In one favorable ~ , the additive contains gluconic acid, lactic acid and citric acid or water-soluble salts thereof in a ratio by weight of 1:
(0.5 to 1.5): ~.5 to 1.5) and preferably in a ratio by weight of 1: (0.7 to 1.0): (0.8 to 1.2).
Suitable rhnsrhnn i c acids are mentioned in DE-C-23 25 829. Accordingly, the rhosphnn;c acids of group b) or water-soluble salts thereof are preferably selected from the following groups:
formula (I): 1-aminoethane-l, 1-diphosphonic acid and 1-lly-lLu-~y~thane-l,l-diphosphonic acid, formula (II): ethyl~n~a;Am;nP tetramethylene rhnsphoni~--acid, diethylenetriamine pentamethylene rhoArhnn; c acid, aminotri- ( 2-propylene-2-rhocrhnn ; -! acid), aminotrimethy-lene rhnsrhnn;c acid, formula (III): rhosrhnnncuccinic acid, methyl rhncrhnnn-5ll~ C;n;c acid, 2-rho5rhnnnhutane-1,2,4-tricarboxylic acid .
In another advantageous: a;_ L, ~he additive ~ontains pllo:,yhu~lic acids or water-soluble salts thereof corresponding to general formula (I) and/or (III), at least one phosphonic acid corr~qpnnlal; n~ to each of formulae (I) and (III), more especially 1-hydroxyethane-1, l-ra~ i rhnsrhon; c acid and 2-phosphonobutane-1, 2, 4-tri-carboxylic acid, preferably being used.
A preferred additive is characterized in that it contains a rhncrhnn;~ acid or water-soluble salts thereof ~:ULL~ u~ ;n~ to each of general formulae (I) and (III) in a ratio by weight of 1:10 to 10:1, preferably in a 35 ratio by weight of 1:1 to 10:1 and more preferably in a ratio by weight of 6 :1 to 9: l .
It has proved to be of advantage to establish certain ratios by weight between the total eontent of earboxylic acids of group a) and the total content of 5 rhfl5rh~nic acids of group b). Particularly favorable glass corrosion values were observed when the ratio by weight of the carboxylic acids of group a) to the phos-phonic acids of group b) is in the range from 1:1 to 5:1 and preferably in the range from 2 :1 to 4 :1.
The effect according to the invention is actually achieved when the additive contains only water besides the above-mentioned: -npllts from groups a) and b).
r~PrPn~l;ng on the application conditions, however, it can be of advantage to add other ~ ries to the water 15 phase of the additive. These include in particular defoamers to eontrol the foam whieh is often formed in the washing of glass bottles eontaining protein~ceoll~
80ils. Aeeordingly, a defoamer solution is preferably used as the aqueous solution e), in whieh ease it is 20 I-:!C ~d in aecordanee with the invention that the defoamer should make up from 1 to 25% by weight, prefer-ably from lO to 20~ by weight and more preferably from 13 to 1896 by weight of the additive as a whole.
The defoamer may be empirically selected according 25 to the types of soil on the glass bottles. Polyglycol ethers of the type rec ~n~lPd in ~P-~-124 815 as foam-suppressing additives in low-foam cleaning formulations have been successfully used. Accordingly, the defoamer is preferably selected from the group of polyethylene 30 glycol ethers C01 r e~c,llding to general formula (IV):
R~--0--( CH2--CH2--0 ) n--R5 ( IV ) in which R4 is a linear or branched alkyl or alkenyl 35 radical containing 8 to 18 carbon atoms, n is a number of . 2~ 763~6 . .
ro 95/13350 10 PCT/EP94/03C18 7 to 12 and preferably 8 to 10 and R5 is an alkyl radical containing 4 to 8 carbon atoms and more especially 4 carbon atoms.
It is known that other surface-active ~ rieS, for example those having a favorable effect on the separation behavior of labels, can be added to the ~l-Anin~ solutions for bottle washing t--rh;nP5. Nonionic surfactants based on ethoxylation and/or propoxylation products of fatty alcohols or fatty amines can be used for this purpose. A particularly suitable group of products based on ethoxylated fatty amines is described in the above-cited DE-A-36 03 57~. The fatty amine ethoxylates described therein are also suitable as auxiliaries for increasing the cleaning performance of the additives according to the invention. Reaction products of fatty amines containing 10 to 18 carbon atoms with 8 to 16 moles of ethylene oxide are particularly suitable as surface-active auxiliaries. In one favorable ';~ L, the nonionic surfactant(s) is/a~e present in the aqueous solution c) in such a quantity that they make up from 1 to 6% by weight and preferably from 2 to 4% by weight of the addlitive as a whole.
The polyether chain - obtained by alkoxylation - of the defoaming and surface-active ~ r; 1 ;Aries may be present in the conventional homolog distribution or in the so-called "narrow-range" homolog distribution. One method of producing narrow-range alkoxylation products is described, for example, in DE-A-38 43 713.
In order to facilitate analysis and establ; L of the concentration of active substances in the cleaning bath, it is helpful if the ready-to-use cleaning solution or the concentrated additive therefor contains tracer substances readily det~rm~n~hle by analysis. One example of such a tracer substance is a soluble lodide, more ~specially potassium iodide, of which the content in the 2 ~ 76336 . .
bath solution may readily be det~rm; nPd by iodometric titration. Accordingly, the additive preferably contains such a tracer substance in a concentration which can readily be determined in the dilute bath solution, but which does not lead to applicational or wastewater problems. For example, the additive according to the invention may contain 0 .1 to 0 . 596 by weight of potassium iodide .
In another ;- L, the invention relates to the use of the additive in an aqueous cleaning solution containing alkali metal hydroxide for the machine washing of glass bottles. The use according to the invention is characterized in that the cleaning solution has a content of active substances which can be adjusted by adding the additive described above to the cleaning solution in such quantities that the content of carboxylic acids o~ group a) in the ~lP~n;~q solution is from 100 to 1,000 mg/l, preferably from 200 to 800 mg/l and more preferably from 300 to 600 mg/l while the content of rhrlsrhrln;c acids o~
group b) is from 50 to 400 mg/l and preferably from 75 to 200 mg/l. The NaOH content of the cleaning solution is in the usual range of 0 . 5 to 5% by weight and preferably l to 3% by weight.
In one advantageous: --;r-nt o~ the use according to the invention, the additive described above, which is formulated as a c:onc~.LL~te of active substances, is added in the appropriate dosage to the cleaning solution containing alkali metal hydroxide. However, the indivi-dual active substances may of course also be separately added to the rlP~n;nq solution in the concentration ranges mentioned above. By comparing the collc~:~lL, ~ltions of the active substances of groups a) and bJ in the ~inal cleaning solution and in the additive, it is readily possible to calculate the concentrations of the other auxiliaries, nonionic surfactants, defoamer~ and tracers ~ t 763~6 established by corresponding dilution of the additive.
The use according to the invention is further characterized in that the bottles are contacted with the cleaning solution over a period of 1 to 30 minutes and 5 preferably over a period of 3 to 20 minutes at tempera-tures of 40 to 90-C and preferably at temperatures of 55 to 85 C.
Example~
The invention is illustrated by the ~ollowing Examples. To determine the relative corrosion rate of glass bottles with cleaning solutions according to the invention and with comparison solutions, new 0.33 liter glass bottles (so-called Vichy bottles) were; sed in 15 the particular solutions for 24 hours at 80-C and the weight loss was detPrm;nPcl in grams of material removed per bottle. Even though these experimental conditions do not ~oLL~:,yu~d to the condltions prevailing in an indus-trial bottle washing plant, the relative corrosive effect 20 of the individual solutions can nevertheless be deter-mined .
In order to standardize the conditions, the test solutions (except for comparison 1) contained 2% by weight of sodium carbonate to simulate the conditions 25 prevailing in industrial baths. In practice, the sodium carbonate content of the cleaning solutions is subject to significant variation. All the test solutions contained 2.5% by weight of NaOH, the ~ ~nPnts listed in Table 1 and water to 100%. Comparison solution 1 was carbonate-30 free.
The test results are set out in Table 1.
Example~ 14 to 18 Additive concentrates were prepared in the form of 35 aqueous solutions for addition to aqueous :llk:~l inP
` 2 1 763~6 WO 95/13350 13 PCT/EPg~/03618 solutions for machine bottle washing by initially intro-ducing the nPcP~Ary quantity of water and then dissolv-ing the other components therein with stirring at room temperature. A to R have the same meaning as in Table 1, 5 L stands for potassium iodide. The contents of active substances and Aln~; 1 i Aries in the additive are shown in 9~ by weight; the balance to 100% by weight is water.
A B C F G H I K L
Example 14 7 - 7 0 . 4 4 - - - 0 . 25 Examplc 15 6 2 6 0 . 5 3 . 9 0 .1 13 5 0 . 25 15 Example 16 5 4 5 0.5 3.9 0.1 13 5 0.25 Example 16 5 4 5 0 . 5 3 . 9 - 15 3 Example 17 6 5 6 0 . 5 4 - 15 3 0. 25 Example 18 5 4 5 1. 5 3 - 13 5 . . . 2 7 76336 X X X X X X X X X X X X X ~ 3 ,~ g 3 3 ~ 3 3 3 3 g' o ~ 1' 1' I' O ~ ~ ~ I' ..
`, g ~ o o o u~ n ~ ~ o ul o o ~n ~ o o o o o o o ~n o o o o oooo o o ~n o o o ~ n o o o o o I 1 1. 1 1 1-- I I I I I I I
o O ~D
s. ~ ~ ~ ~n ~n ul ~ ~ ~ W ul ~ o ~
o o `
o ~
w l l l l W I I I I I I I I I I I w I I ~ 3 I I I I CO I I I I I I I I I I I I I I I I I I `-O ~h o o o o o o o o o o o o o o o o o o o o o o o o o W 1~ W ~I N i' 1' 1' W UWP ~ ~P W ~ 0~ Ul ~1 0~ I~J
O ~;1 ~ ~) ~J ~D O N O O O W ~ ~ Ul N r~
C~
.
~ 2 1 ~6336 H ~ ~ ~ 2 o Q n ~3 o Q Q l_ X ' - ' Q S~. ~ Q
' Y
X
O ~
X ~ . , ~D '' X Q ' P. ~
~' Q
o
, , ENGLIS~ TRAN.~.ATTON
OF INTERNATIONAL APPLICATION
An additive for the washing of glass bottle~ and it~ u~
~or reducing gla~s corrosion This invention relates to a new additive for ag,ueous ;llks~l in~ solutions for bottle washing ~-~hinPc for washing glass bottles, more especially beverage bottles.
The function of the additive is to reduce the corrosion 5 of glass which normally occurs under alkaline bottle washing conditions. The invention also relates to the use of the additive in aqueous solutions for the machine washing of glass bottles.
Before reusable beverage bottles of glass are 10 refilled, the labels have to be removed and the bottles thoroughly washed. ~ighly ;~lks~l;nF~ detergent solutions containing sodium hydroxide are normally used for this purpose in the bottle washing machines of bottling fac-tories. The alkali metal hydroxide content is normally in the range from 0 . 5 to 596 by weight and more especially in the range from 1 to 3~6 by weight. Providing suitable products and processes are used, the required cleaning effect is achieved. An unwanted effect in bottle washing is corrosion of the glass. This is a rh~nl nn by which 20 the surface of the glass bottles is chemically attacked, resulting in surface~ roughness. Secondary rhen -n~
often include difficulties in cleaning the rough surface and the danger of microorganism growth in cracks and holes in the surface. It is known from practical experi-25 ence and from laboratory tests that the corrosiveness ofthe cleaning solutions containing sodium hydroxide is increased by an increased percentage content of sodium carbonate .
Since the number of possible rf~f i 11; n~ cycles for 30 reusable glass bottles is limited ~nter alia by the corrosion of glass during the cleaning process, there is ` ~ 2 ~ 7~336 a need for additives which reduce the corrosion of glass in cleaning solutions. Accordingly, the problem ad-dressed by the present invention was to provide a combi-nation of active substances for aqueous Alk~l inP cleaning solutions for the machine washing of glass bottles which, in addition to enhancing the cleaning properties, would contribute towards reducing glass corrosion.
Another problem addressed by the present invention was to formulate this combination of active substances as a concentrate which could be added in situ to the aqueous alkaline cleaning solution.
Aliphatic 11YdLU~Y Ir, lly~lLUXydi- or hydroxytri-carboxlyic acids containing 3 to 6 carbon atoms and l to 5 hydroxy groups are known as ~ onPnts of industrial detergents . It is also known ~hat geminal dirhosrhnn; c acids ~OLL'~ r'~liTl~ to general formula (I) below, amino-methylene ~h~srh~n;c acids corresponding to general for-mula (II) below or rho~rhnnncarboxylic acids c ULLe-~Ulld ing formula (III) below can be added to cleaning solu-tions. It is assumed that the acids mentioned or rather their anions have complexing properties, especially towards the ions r~crnn~:ihle for the hardness of water.
In addition, the rhosrhnn;~ and rho~rhonncarboxylic acids mentioned show so-called scale-inhibiting properties.
DB-C-23 25 829, for example, describes a sequester-ing agent for divalent and trivalent cations in the form of a mixture of l-l~y~lLu~yt:Lhane-~ ;rhosrhnn;c acid, aminotrimethylene rhosrhnn; c acid and 2-rhosrh~nnhutane 1, 2, 4-tricarboxylic acid or water-soluble salts thereof .
This flo~_ I contains details as to which geminal ~;rhncrhnn;C acids, Am;n~ thylene phosphonic acids and rh~srhonc rArboxylic acids may be used as the combination of sequestering agents. The phosphonic acids mentioned in this document, which is hereby included as part of the disclosure of the present invention, are also suitable as ~ ~ 76336 WO 95/13350 3 PCq~/EP94/03618 rhosrhnn;~- acid components for the purposes of the present invention.
The use of hydroxyalkane oligocarboxylic acids as complexing agents in industrial alkaline cleaners is also known. For example, WO 92/0882~ describes a water-containing Alk~linP cleaner for aluminium with a pH value of 10 to 12 which contains an alkaline builder: -nt, Aminn~lkyl or lly~lLuxyclkyl ~l;rht~qrh~ln;c acids, surfac-tants and complexing agents for aluminium. Gluconates and tartrates inter alia are mentioned as complexing agents for aluminium. Hitherto unpublished German patent application P ~2 32 612.5 describes the use of a combina-tion of a rhosrhn~;c acid, an o~;tll~;n~ agent and at least one short-chain organic carboxylic acid selected from inter alia tartaric acid and citric acid in acidic aqueous solutions with a pH value of 0 to 3 for the removal of magnetite coatings in water-carrying systems.
DE:-A-36 03 579 describes acidic cleaning concen-trates containing phosphoric acid in which ethoxylated fatty amines corr~spnnr9in~ to general formula (V) are present as a key constituent:
Rb I
25 R~--N--(CH2--CH2--O) nH (V) In this formula, n is an integer of 2 to 3 0, R" is a linear or branched, saturated or unsaturated alkyl 30 radical containing 8 to 24 carbon atoms and Rl' is a -(CH2-CH2-O)m-H group or a ~ ~ 76336 . .
W0 95/13350 4 PCT/~P94/03618 (CH2-CH~-O) x-H
--R'--N
(CH2-CH2--0) y~H
group, where R~ is an alkylene radical containing 2 to 6 carbon atoms, m, x and y are each numbers of o to 30.
The concentrates also contain a combination of different rhncrhr~nic acids corresponding to general formulae I, II and III below and, in some cases, gluconic acid. The total phosphonic acid content is greater than the gluconic acid content.
German patent application P 43 24 396.7 describes cleaning formulations of high wetting power which are preferably used for cleaning plastic surfaces. They contain as key constituents -- o~mi nn- or diamino or -dicarboxylic acids or amides thereof in combination 20 with relatively long-chain carboxylic acids and nnn;c-nir~
surfactants. These cleaners may contain as optional r-nts llydLu~cyyolycarboxylic acids, such as tartaric acid and citric acid, geminal rl;rhosrhnn;c acids, such as 1 hydL~ ,cy~Lhane-1,1-(l;rhnc:rhnn;c acid, ~m;norhnsrhonic 25 acids and phosrh- nnpolycarboxylic acids. These cleaners may also contain alkali metal hydroxides as builders.
It has surprisingly been found a combination of llydLu~Ly~ligocarboxylic acids and rhosrhnn; c acids known as sequestrants in certain quantity ratios distinctly 30 reduces the corrosion of glass caused by ~lk~l;n~ carbon-ate-containing cleaning solutions. The well-known complexing properties of these active substances had actually been expected to increase the corrosion rate.
In a first .omho~ L, the present invention relates 35 to an additive in the form of an aqueous solution for addition to i~lk~ nF~ cleaning baths for the machine . .. 21 76336 . , washing of glass bottles, consisting of a~ 7 to 25$ by weight, based on the free acid, of one or more aliphatic hydLuxy n~ ydLuxydi- or llydLu~syl-Licar~oxylic acids containing 2 to 6 carbon atoms and 1 to 5 hydroxy groups and/or aliphatic r nAminn- or diamino-mono- or -dicarboxylic acids containing 2 to 6 carbon atoms or water-soluble salts thereof, 10 b) 1 to 12% by weight, based on the free acid, of one or more geminal rl;crhnsrhnn;~ acids corrPcro~ n~ to general formula (I~:
O R O
5HO -- P -- C -- P -- OH ( I ) l l l OH Z OH
in which R is an alkyl radical containing 1 to 5 carbon atoms and Z is 5lydLvg~5l~ a hydroxy group or an amino group, and/or one or more Am;r thylene rh~Erhnn;~ acids c,LL~ L,~ 7;n~J to general formula (II):
Rl - CXY
N -- CXY - R3 ( II ) 3 0 R2 _ CXY
in which X and Y ; n~rPn~lPntly of one another represent hydrogen or an alkyl group containing 1 to 4 carbon atoms, Rl and R2 represent -PO~H2 or a group u uLLt~ ullding to 2 t 76336 the formula H203P - CH2 H203P - CH~
and R3 representS -PO3H2 and/or one or more phosphonocarboxylic acids corre-sponding to general formula (III):
R' I
H203P -- C - COOH (III) I
in which R' is hydrogen, an alkyl group containing 1 to 4 carbon atoms or a -CH2-CH2-COOH group, or water-soluble salts thereof, c) 63 to 92~6 by weight of water or an aqueous 601ution of other ~IlYil;~ries~
the total concentration of the ~arboxylic acids of group a) being no lower than the total .;ul-c~ Lc-tion of the 25 rhrsrhnnic acids of group b).
The additive preferably contains 10 to 20~6 by weight, based on the free aci~, of one or more of the carboxylic acids of group a) or water-soluble salts thereof and/or, preferably and, 2 to 6% by weight, based 30 on the free acid, of one or more of the rhoqrhon;~ acids of group b) or water-soluble salts thereof and 68 to 91%
by weight and preferably 74 to ~38% by weight of water or an a~ueous solution of other auxiliaries.
Since the additive is intended for addition to an 35 llk~l ;n~ cleaning solution, the acids suitable for use in accordance with the invention are present in the in-use solution in the form of their anions irrespective of ` 2~ 76336 . .
whether the additive contains them as free acids or as water-soluble salts. I~ the carboxylic acids of group a) and/or the rhosrhnn; c acids of group b) are used as water-soluble salts, the alkali metal or ammonium salts 5 are particularly suitable, sodium salts preferably being used. The expression "water-soluble" in this regard means that the salts are soluble in the aqueous phase of the additive in the concentration ranges mentioned above, based on the free acids.
Suitable lly~Lu.cy-~.rboxylic acids of group a) are, in particular, hydroxyacetic acid, lactic acid, gluconic acid, tartronic acid, malic acid, tartaric acid and citric acid. Aminocarboxylic acids of group a) are also suitable for the purposes of the invention. The natu-15 rally occurring alpha-amino acids or amino acid deriva-tives are generally chiral in relation to the carbon atom carrying the amino group and are present in the L-form.
Although the chiral L-amino acids do not afford any particular advantages for the t~-hnic~l application 20 according to the invention, they are preferably used as natural active substances or as active substances identi-cal with those occurring in nature. Accordingly, the following amino acids, for example, may be used in the form of their racemates or in optically active form:
25 glycine, alanine, valine, leucine, isoleucine, beta-alanine, gamma-aminobutyric acid, epsilon-aminocaproic acid, glutamine, glutamic acid, aspartic acid, amino-malonic acid, ~m~no~lipic acid and 2-amino-2-methylpen-tanedioic acid. The amino acids may additionally bear 30 hydroxyl groups. Examples of corr~spnr~linq amino acid6 are serine and threonine.
In one particularly advantageous - 'i- 1, the additive contains 2 to 4 and preferably 3 different carboxylic acids, more esp~ lly ~ly.lL~Ly-cLrboxylic acids 35 of group a), the combination of gluconic acid, lactic acid and citric acid leading to particularly positive results. In one favorable ~ , the additive contains gluconic acid, lactic acid and citric acid or water-soluble salts thereof in a ratio by weight of 1:
(0.5 to 1.5): ~.5 to 1.5) and preferably in a ratio by weight of 1: (0.7 to 1.0): (0.8 to 1.2).
Suitable rhnsrhnn i c acids are mentioned in DE-C-23 25 829. Accordingly, the rhosphnn;c acids of group b) or water-soluble salts thereof are preferably selected from the following groups:
formula (I): 1-aminoethane-l, 1-diphosphonic acid and 1-lly-lLu-~y~thane-l,l-diphosphonic acid, formula (II): ethyl~n~a;Am;nP tetramethylene rhnsphoni~--acid, diethylenetriamine pentamethylene rhoArhnn; c acid, aminotri- ( 2-propylene-2-rhocrhnn ; -! acid), aminotrimethy-lene rhnsrhnn;c acid, formula (III): rhosrhnnncuccinic acid, methyl rhncrhnnn-5ll~ C;n;c acid, 2-rho5rhnnnhutane-1,2,4-tricarboxylic acid .
In another advantageous: a;_ L, ~he additive ~ontains pllo:,yhu~lic acids or water-soluble salts thereof corresponding to general formula (I) and/or (III), at least one phosphonic acid corr~qpnnlal; n~ to each of formulae (I) and (III), more especially 1-hydroxyethane-1, l-ra~ i rhnsrhon; c acid and 2-phosphonobutane-1, 2, 4-tri-carboxylic acid, preferably being used.
A preferred additive is characterized in that it contains a rhncrhnn;~ acid or water-soluble salts thereof ~:ULL~ u~ ;n~ to each of general formulae (I) and (III) in a ratio by weight of 1:10 to 10:1, preferably in a 35 ratio by weight of 1:1 to 10:1 and more preferably in a ratio by weight of 6 :1 to 9: l .
It has proved to be of advantage to establish certain ratios by weight between the total eontent of earboxylic acids of group a) and the total content of 5 rhfl5rh~nic acids of group b). Particularly favorable glass corrosion values were observed when the ratio by weight of the carboxylic acids of group a) to the phos-phonic acids of group b) is in the range from 1:1 to 5:1 and preferably in the range from 2 :1 to 4 :1.
The effect according to the invention is actually achieved when the additive contains only water besides the above-mentioned: -npllts from groups a) and b).
r~PrPn~l;ng on the application conditions, however, it can be of advantage to add other ~ ries to the water 15 phase of the additive. These include in particular defoamers to eontrol the foam whieh is often formed in the washing of glass bottles eontaining protein~ceoll~
80ils. Aeeordingly, a defoamer solution is preferably used as the aqueous solution e), in whieh ease it is 20 I-:!C ~d in aecordanee with the invention that the defoamer should make up from 1 to 25% by weight, prefer-ably from lO to 20~ by weight and more preferably from 13 to 1896 by weight of the additive as a whole.
The defoamer may be empirically selected according 25 to the types of soil on the glass bottles. Polyglycol ethers of the type rec ~n~lPd in ~P-~-124 815 as foam-suppressing additives in low-foam cleaning formulations have been successfully used. Accordingly, the defoamer is preferably selected from the group of polyethylene 30 glycol ethers C01 r e~c,llding to general formula (IV):
R~--0--( CH2--CH2--0 ) n--R5 ( IV ) in which R4 is a linear or branched alkyl or alkenyl 35 radical containing 8 to 18 carbon atoms, n is a number of . 2~ 763~6 . .
ro 95/13350 10 PCT/EP94/03C18 7 to 12 and preferably 8 to 10 and R5 is an alkyl radical containing 4 to 8 carbon atoms and more especially 4 carbon atoms.
It is known that other surface-active ~ rieS, for example those having a favorable effect on the separation behavior of labels, can be added to the ~l-Anin~ solutions for bottle washing t--rh;nP5. Nonionic surfactants based on ethoxylation and/or propoxylation products of fatty alcohols or fatty amines can be used for this purpose. A particularly suitable group of products based on ethoxylated fatty amines is described in the above-cited DE-A-36 03 57~. The fatty amine ethoxylates described therein are also suitable as auxiliaries for increasing the cleaning performance of the additives according to the invention. Reaction products of fatty amines containing 10 to 18 carbon atoms with 8 to 16 moles of ethylene oxide are particularly suitable as surface-active auxiliaries. In one favorable ';~ L, the nonionic surfactant(s) is/a~e present in the aqueous solution c) in such a quantity that they make up from 1 to 6% by weight and preferably from 2 to 4% by weight of the addlitive as a whole.
The polyether chain - obtained by alkoxylation - of the defoaming and surface-active ~ r; 1 ;Aries may be present in the conventional homolog distribution or in the so-called "narrow-range" homolog distribution. One method of producing narrow-range alkoxylation products is described, for example, in DE-A-38 43 713.
In order to facilitate analysis and establ; L of the concentration of active substances in the cleaning bath, it is helpful if the ready-to-use cleaning solution or the concentrated additive therefor contains tracer substances readily det~rm~n~hle by analysis. One example of such a tracer substance is a soluble lodide, more ~specially potassium iodide, of which the content in the 2 ~ 76336 . .
bath solution may readily be det~rm; nPd by iodometric titration. Accordingly, the additive preferably contains such a tracer substance in a concentration which can readily be determined in the dilute bath solution, but which does not lead to applicational or wastewater problems. For example, the additive according to the invention may contain 0 .1 to 0 . 596 by weight of potassium iodide .
In another ;- L, the invention relates to the use of the additive in an aqueous cleaning solution containing alkali metal hydroxide for the machine washing of glass bottles. The use according to the invention is characterized in that the cleaning solution has a content of active substances which can be adjusted by adding the additive described above to the cleaning solution in such quantities that the content of carboxylic acids o~ group a) in the ~lP~n;~q solution is from 100 to 1,000 mg/l, preferably from 200 to 800 mg/l and more preferably from 300 to 600 mg/l while the content of rhrlsrhrln;c acids o~
group b) is from 50 to 400 mg/l and preferably from 75 to 200 mg/l. The NaOH content of the cleaning solution is in the usual range of 0 . 5 to 5% by weight and preferably l to 3% by weight.
In one advantageous: --;r-nt o~ the use according to the invention, the additive described above, which is formulated as a c:onc~.LL~te of active substances, is added in the appropriate dosage to the cleaning solution containing alkali metal hydroxide. However, the indivi-dual active substances may of course also be separately added to the rlP~n;nq solution in the concentration ranges mentioned above. By comparing the collc~:~lL, ~ltions of the active substances of groups a) and bJ in the ~inal cleaning solution and in the additive, it is readily possible to calculate the concentrations of the other auxiliaries, nonionic surfactants, defoamer~ and tracers ~ t 763~6 established by corresponding dilution of the additive.
The use according to the invention is further characterized in that the bottles are contacted with the cleaning solution over a period of 1 to 30 minutes and 5 preferably over a period of 3 to 20 minutes at tempera-tures of 40 to 90-C and preferably at temperatures of 55 to 85 C.
Example~
The invention is illustrated by the ~ollowing Examples. To determine the relative corrosion rate of glass bottles with cleaning solutions according to the invention and with comparison solutions, new 0.33 liter glass bottles (so-called Vichy bottles) were; sed in 15 the particular solutions for 24 hours at 80-C and the weight loss was detPrm;nPcl in grams of material removed per bottle. Even though these experimental conditions do not ~oLL~:,yu~d to the condltions prevailing in an indus-trial bottle washing plant, the relative corrosive effect 20 of the individual solutions can nevertheless be deter-mined .
In order to standardize the conditions, the test solutions (except for comparison 1) contained 2% by weight of sodium carbonate to simulate the conditions 25 prevailing in industrial baths. In practice, the sodium carbonate content of the cleaning solutions is subject to significant variation. All the test solutions contained 2.5% by weight of NaOH, the ~ ~nPnts listed in Table 1 and water to 100%. Comparison solution 1 was carbonate-30 free.
The test results are set out in Table 1.
Example~ 14 to 18 Additive concentrates were prepared in the form of 35 aqueous solutions for addition to aqueous :llk:~l inP
` 2 1 763~6 WO 95/13350 13 PCT/EPg~/03618 solutions for machine bottle washing by initially intro-ducing the nPcP~Ary quantity of water and then dissolv-ing the other components therein with stirring at room temperature. A to R have the same meaning as in Table 1, 5 L stands for potassium iodide. The contents of active substances and Aln~; 1 i Aries in the additive are shown in 9~ by weight; the balance to 100% by weight is water.
A B C F G H I K L
Example 14 7 - 7 0 . 4 4 - - - 0 . 25 Examplc 15 6 2 6 0 . 5 3 . 9 0 .1 13 5 0 . 25 15 Example 16 5 4 5 0.5 3.9 0.1 13 5 0.25 Example 16 5 4 5 0 . 5 3 . 9 - 15 3 Example 17 6 5 6 0 . 5 4 - 15 3 0. 25 Example 18 5 4 5 1. 5 3 - 13 5 . . . 2 7 76336 X X X X X X X X X X X X X ~ 3 ,~ g 3 3 ~ 3 3 3 3 g' o ~ 1' 1' I' O ~ ~ ~ I' ..
`, g ~ o o o u~ n ~ ~ o ul o o ~n ~ o o o o o o o ~n o o o o oooo o o ~n o o o ~ n o o o o o I 1 1. 1 1 1-- I I I I I I I
o O ~D
s. ~ ~ ~ ~n ~n ul ~ ~ ~ W ul ~ o ~
o o `
o ~
w l l l l W I I I I I I I I I I I w I I ~ 3 I I I I CO I I I I I I I I I I I I I I I I I I `-O ~h o o o o o o o o o o o o o o o o o o o o o o o o o W 1~ W ~I N i' 1' 1' W UWP ~ ~P W ~ 0~ Ul ~1 0~ I~J
O ~;1 ~ ~) ~J ~D O N O O O W ~ ~ Ul N r~
C~
.
~ 2 1 ~6336 H ~ ~ ~ 2 o Q n ~3 o Q Q l_ X ' - ' Q S~. ~ Q
' Y
X
O ~
X ~ . , ~D '' X Q ' P. ~
~' Q
o
Claims (18)
1. An additive in the form of an aqueous solution for addition to alkaline cleaning baths for the machine washing of glass bottles, consisting of a) 7 to 25% by weight, based on the free acid, of one or more aliphatic hydroxymono-, hydroxydi- or hydroxytricarboxylic acids containing at least 2 and up to 6 carbon atoms and 1 to 5 hydroxy groups and/
or aliphatic monoamino-monocarboxylic acids or -dicarboxylic acids or diamino-monocarboxylic acids or -dicarboxylic acids containing at least 2 and up to 6 carbon atoms or water-soluble salts thereof, b) 1 to 12% by weight, based on the free acid, of one or more geminal disphosphonic acids corresponding to general formula (I):
(I) in which R is an alkyl radical containing 1 to 5 carbon atoms and Z is hydrogen a hydroxy group or an amino group, and/or one or more aminomethylene phosphonic acids corresponding to general formula (II):
(II) in which X and Y independently of one another represent hydrogen or an alkyl group containing 1 to 4 carbon atoms, R1 and R2 represent -PO3H2 or a group corresponding to the formula and R3 represents -PO3H2 and/or one or more phosphonocarboxylic acids corre-sponding to general formula (III):
(III) in which R' is hydrogen, an alkyl group containing 1 to 4 carbon atoms or a -CH2-CH2-COOH group, or water-soluble salts thereof, c) 63 to 92% by weight of water or an aqueous solution of other auxiliaries, the total concentration of the carboxylic acids of group a) being no lower than the total concentration of the phosphonic acids of group b).
or aliphatic monoamino-monocarboxylic acids or -dicarboxylic acids or diamino-monocarboxylic acids or -dicarboxylic acids containing at least 2 and up to 6 carbon atoms or water-soluble salts thereof, b) 1 to 12% by weight, based on the free acid, of one or more geminal disphosphonic acids corresponding to general formula (I):
(I) in which R is an alkyl radical containing 1 to 5 carbon atoms and Z is hydrogen a hydroxy group or an amino group, and/or one or more aminomethylene phosphonic acids corresponding to general formula (II):
(II) in which X and Y independently of one another represent hydrogen or an alkyl group containing 1 to 4 carbon atoms, R1 and R2 represent -PO3H2 or a group corresponding to the formula and R3 represents -PO3H2 and/or one or more phosphonocarboxylic acids corre-sponding to general formula (III):
(III) in which R' is hydrogen, an alkyl group containing 1 to 4 carbon atoms or a -CH2-CH2-COOH group, or water-soluble salts thereof, c) 63 to 92% by weight of water or an aqueous solution of other auxiliaries, the total concentration of the carboxylic acids of group a) being no lower than the total concentration of the phosphonic acids of group b).
2. An additive as claimed in claim 1, characterized in that it consists of 10 to 20% by weight, based on the free acid, of one or more of the carboxylic acids of group a) or water-soluble salts thereof and 2 to 6% by weight, based on the free acid, of one or more of the phosphonic acids of group b) or water-soluble salts thereof and 74 to 88% by weight of water or an aqueous solution of other auxiliaries.
3. An additive as claimed in one or both of claims 1 and 2, characterized in that alkali metal or ammonium salts, preferably sodium salts, are used as the water-soluble salts of the carboxylic acids of group a) and/or the phosphonic acids of group b).
4. An additive as claimed in one or more of claims 1 to 3, characterized in that the hydroxycarboxylic acids of group a) are selected from hydroxyacetic acid, lactic acid, gluconic acid, tartronic acid, malic acid, tartaric acid and citric acid.
5. An additive as claimed in one or more of claims 1 to 3, characterized in that the aminocarboxylic acids of group a) are selected from glycine, alanine, .beta.-alanine, valine, leucine, isoleucine, .gamma.-aminobutyric acid, .epsilon.-aminocaproic acid, glutamine, glutamic acid, aspartic acid, aminomalonic acid, aminoadipic acid and 2-amino-2-methylpentanedioic acid.
6. An additive as claimed in one or more of claims 1 to 3, characterized in that the amino acids of group a) carry additional hydroxyl groups and are preferably selected from serine and threonine.
7. An additive as claimed in one or more of claims 4 to 6, characterized in that it contains 2 to 4. and prefer-ably 3 different carboxylic acids, preferably hydroxycar-boxylic acids, more particularly gluconic acid, lactic acid and citric acid, or water-soluble salts thereof.
8. An additive as claimed in claim 7, characterized in that it contains gluconic acid, lactic acid and citric acid or water-soluble salts thereof in a ratio by weight of 1: (0.5 to 1.5): (0.5 to 1.5) and preferably in a ratio by weight of 1 : (0.7 to 1.0) : (0.8 to 1.2).
9. An additive as claimed in one or more of claims 1 to 8, characterized in that the phosphonic acids of group b) or water-soluble salts thereof are selected from the following groups:
formula (I): 1-aminoethane-1,1-diphosphonic acid and 1-hydroxyethane-1,1-diphosphonic acid, formula (II): ethylenediamine tetramethylene phosphonic acid, diethylenetriamine pentamethylene phosphonic acid, aminotri-(2-propylene-2-phosphonic acid), aminotrimethy-lene phosphonic acid, formula (III): phosphonosuccinic acid, methyl phosphono-succinic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid.
formula (I): 1-aminoethane-1,1-diphosphonic acid and 1-hydroxyethane-1,1-diphosphonic acid, formula (II): ethylenediamine tetramethylene phosphonic acid, diethylenetriamine pentamethylene phosphonic acid, aminotri-(2-propylene-2-phosphonic acid), aminotrimethy-lene phosphonic acid, formula (III): phosphonosuccinic acid, methyl phosphono-succinic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid.
10. An additive as claimed in claim 9, characterized in that it contains phosphonic acids or water-soluble salts thereof corresponding to general formula (I) and/or (III), at least one phosphonic acid corresponding to each of formulae (I) and (III), more especially 1-hydroxy-ethane-1,1-diphosphonic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid, preferably being used.
11. An additive as claimed in claim 10, characterized in that it contains a phosphonic acid or water-soluble salts thereof corresponding to each of general formulae (I) and (III) in a ratio by weight of 1:10 to 10:1, preferably in a ratio by weight of 1:1 to 10:1 and more preferably in a ratio of 6:1 to 9:1.
12. An additive as claimed in one or more of claims 1 to 11, characterized in that the ratio by weight of the carboxylic acids of group a) to the phosphonic acids of group b) is 1:1 to 5:1 and preferably 2:1 to 4:1.
13. An additive as claimed in one or more of claims 1 to 12, characterized in that a defoamer solution is used as the aqueous solution c).
14. An additive as claimed in claim 13, characterized in that the defoamer makes up from 1 to 25% by weight, preferably 10 to 20% by weight and more preferably 13 to 18% by weight of the additive as a whole.
15. An additive as claimed in one or both of claims 13 and 14, characterized in that the defoamer is selected from the group of polyethylene glycol ethers correspond-ing to general formula (IV):
R4-O-(CH2-CH2-O)n-R5 (IV) in which R4 is a linear or branched alkyl or alkenyl radical containing 8 to 18 carbon atoms, n is a number of 7 to 12 and preferably 8 to 10 and R5 is an alkyl radical containing 4 to 8 carbon atoms and more especially 4 carbon atoms.
R4-O-(CH2-CH2-O)n-R5 (IV) in which R4 is a linear or branched alkyl or alkenyl radical containing 8 to 18 carbon atoms, n is a number of 7 to 12 and preferably 8 to 10 and R5 is an alkyl radical containing 4 to 8 carbon atoms and more especially 4 carbon atoms.
16. An additive as claimed in one or more of claims 1 to 15, characterized in that the aqueous solution c) addi-tionally contains one or more nonionic surfactants based on ethoxylation and/or propoxylation products of fatty alcohols or fatty amines, preferably ethoxylation prod-ucts of fatty amines, more especially reaction products of fatty amines containing 10 to 18 carbon atoms with 8 to 16 moles of ethylene oxide, the nonionic surfactant(s) making up from 1 to 6% by weight and preferably from 2 to 4% by weight of the additive as a whole.
17. The use of the additive claimed in one or more of claims 1 to 16 for reducing the corrosion of glass in aqueous cleaning solutions for bottle washing machines having an alkali metal hydroxide content of 0.5 to 5% by weight and preferably 1 to 396 by weight, characterized in that the cleaning solutions have a content of active substances which can be adjusted by adding the additive to the cleaning solution in such quantities that the content of carboxylic acids of group a) in the cleaning solution is from 100 to 1,000 mg/l, preferably from 200 to 800 mg/l and more preferably from 300 to 600 mg/l and the content of phosphonic acids of group b) is from 50 to 400 mg/l and preferably from 75 to 200 mg/l.
18. The use claimed in claim 17, characterized in that the bottles are contacted with the cleaning solution for 1 to 30 minutes and preferably for 3 to 20 minutes at temperatures of 40 to 90°C and preferably at temperatures of 55 to 85°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4338626.1 | 1993-11-12 | ||
| DE4338626A DE4338626A1 (en) | 1993-11-12 | 1993-11-12 | Additive for glass bottle cleaning and its use to reduce glass corrosion |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2176336A1 true CA2176336A1 (en) | 1995-05-18 |
Family
ID=6502420
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002176336A Abandoned CA2176336A1 (en) | 1993-11-12 | 1994-11-03 | Additive for use in glass-bottle washing and its use in decreasing glass corrosion |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0728180B1 (en) |
| AT (1) | ATE170213T1 (en) |
| CA (1) | CA2176336A1 (en) |
| DE (2) | DE4338626A1 (en) |
| DK (1) | DK0728180T3 (en) |
| PL (1) | PL314308A1 (en) |
| WO (1) | WO1995013350A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6835702B2 (en) | 2000-11-07 | 2004-12-28 | Ecolab Inc. | Compositions and methods for mitigating corrosion of applied color designs |
| EP1679361A1 (en) * | 2003-10-27 | 2006-07-12 | Wako Pure Chemical Industries, Ltd. | Cleaning agent for substrate and cleaning method |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19945169C2 (en) * | 1999-09-21 | 2001-09-20 | Tensid Chemie G Maier Gmbh | Process for laminating surface portions and / or fissures of bottles made of glass and corresponding use of a nonionic surfactant solution |
| US6395693B1 (en) | 1999-09-27 | 2002-05-28 | Cabot Microelectronics Corporation | Cleaning solution for semiconductor surfaces following chemical-mechanical polishing |
| AU2001262109A1 (en) * | 2000-05-31 | 2001-12-11 | Unilever Plc | Rinse aid compositions |
| DE10049657C2 (en) * | 2000-10-07 | 2003-02-27 | Henkel Kgaa | Machine dishwashing method and machine dishwashing detergent with improved corrosion protection |
| DE102009025411B4 (en) | 2009-06-16 | 2011-05-19 | Innovent E.V. Technologieentwicklung | Use of zinc dust particles or particulate dust containing zinc or a zinc compound as a corrosion inhibitor for glass |
| PL2924101T3 (en) * | 2014-03-24 | 2021-11-08 | Chemische Fabrik Dr. Weigert Gmbh & Co Kg | Cleaning agent and method for cleaning dishes |
| BE1021365B1 (en) * | 2014-09-01 | 2015-11-06 | Sopura S.A. | ADDITIVE WASH |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3519353A1 (en) * | 1985-05-30 | 1986-12-04 | Henkel KGaA, 4000 Düsseldorf | MELT BLOCK-SHAPED, ALKALINE HYDROXIDE-CONTAINING AGENT FOR THE MACHINE CLEANING OF DISHES AND METHOD FOR THE PRODUCTION THEREOF |
| DE3603579A1 (en) * | 1986-02-06 | 1987-08-13 | Henkel Kgaa | USE OF ETHOXYLATED FAT AMINES AS SOLUTION MEDIATOR |
| EP0476212A1 (en) * | 1990-09-17 | 1992-03-25 | The Procter & Gamble Company | Liquid detergent compositions |
| JP2869834B2 (en) * | 1992-07-17 | 1999-03-10 | 大三工業株式会社 | How to prevent whitening of glass |
| DE4232612A1 (en) * | 1992-09-29 | 1994-03-31 | Henkel Kgaa | Removal of magnetite deposits in water-bearing systems |
-
1993
- 1993-11-12 DE DE4338626A patent/DE4338626A1/en not_active Withdrawn
-
1994
- 1994-11-03 AT AT94931560T patent/ATE170213T1/en not_active IP Right Cessation
- 1994-11-03 CA CA002176336A patent/CA2176336A1/en not_active Abandoned
- 1994-11-03 DE DE59406789T patent/DE59406789D1/en not_active Expired - Lifetime
- 1994-11-03 WO PCT/EP1994/003618 patent/WO1995013350A1/en active IP Right Grant
- 1994-11-03 PL PL94314308A patent/PL314308A1/en unknown
- 1994-11-03 DK DK94931560T patent/DK0728180T3/en active
- 1994-11-03 EP EP94931560A patent/EP0728180B1/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6835702B2 (en) | 2000-11-07 | 2004-12-28 | Ecolab Inc. | Compositions and methods for mitigating corrosion of applied color designs |
| EP1679361A1 (en) * | 2003-10-27 | 2006-07-12 | Wako Pure Chemical Industries, Ltd. | Cleaning agent for substrate and cleaning method |
| EP1679361A4 (en) * | 2003-10-27 | 2010-07-28 | Wako Pure Chem Ind Ltd | Cleaning agent for substrate and cleaning method |
| US8900371B2 (en) | 2003-10-27 | 2014-12-02 | Wako Pure Chemical Industries, Ltd. | Cleaning agent for substrate and cleaning method |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0728180B1 (en) | 1998-08-26 |
| ATE170213T1 (en) | 1998-09-15 |
| DE4338626A1 (en) | 1995-05-18 |
| PL314308A1 (en) | 1996-09-02 |
| WO1995013350A1 (en) | 1995-05-18 |
| DE59406789D1 (en) | 1998-10-01 |
| DK0728180T3 (en) | 1999-06-28 |
| EP0728180A1 (en) | 1996-08-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |