CA1329101C - Zero phosphorus heavy duty laundry detergent composition - Google Patents
Zero phosphorus heavy duty laundry detergent compositionInfo
- Publication number
- CA1329101C CA1329101C CA000609263A CA609263A CA1329101C CA 1329101 C CA1329101 C CA 1329101C CA 000609263 A CA000609263 A CA 000609263A CA 609263 A CA609263 A CA 609263A CA 1329101 C CA1329101 C CA 1329101C
- Authority
- CA
- Canada
- Prior art keywords
- detergent composition
- molecular weight
- water
- alkali metal
- sodium hydroxide
- 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.)
- Expired - Fee Related
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
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- 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
-
- 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
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
Abstract A solid heavy duty laundry detergent composition having a zero phosphorus content is disclosed that has the capability of effectively conditioning service water. The detergent composition comprises a source of alkalinity, a water-conditioning vinyl polymer with pendant carboxyl groups, a water-conditioning copolymer of acrylic acid and itaconic acid, and at least one nonionic surfactant.
Description
~ ~32911 01 ZERO P~OS?~O~lUS ElEAVY DUTY
LAUNr)RY DET~RGENT COI~OSITION
~ield of the _nvention The invention pertalns to a solid heavy duty laundry detergent compGsition having a zero phos~norus content.
More specifically, the in-~ention pertains to a novel heavy duty detergent compositlon that can so~ten (i.e., treat divalent or trivalent hardness lons in) servlce water containing the detersent composition either be.ore or during deter~ent action.
Much attention has been given in recent years to the components o. detergen~s that treat or reduce the harmful effects of water hardness on cleaning compositions and processes. Hardness ions are typically undesirable in conjunction with washing deter~ents since they interfere with the soil removal .~echanism of detergents. Such ions typically comorise metal ions such as calcium, magnesium, iron, manganese, and other typically divalent or trivalent metal cations de?ending on the source of service water used in the washing environment.
In recent years, the use of e'fective concentrations of complex phosphates such as sodium tripolyphosphate, and other sequestrants, in detergents as water softening agents has come under increasing attack due to environmental concerns. PhosDhates have been identified as contributing to excess water eutrophication, a process o.' algae overgrowth in environmental waters. .~any state governments have found it desira~le to cause detergent makers to replace phos~ha~es with components that do not sti~ulate algae growth. Therefore, some states have legislated that detergent compositions have a zero ~hosphorus content.
Currently, there are no phosphorus free heavy duty solid laundry detergent products available in the United States.
Accordingly, a substantial need exists to provide a solid heavy duty laundry detergent without intentionally .
1329~01 added phosphates or phosphorus that has the detergency and water conditioning benefits of phosphorus-containing detergents without the assoclated environmental harm.
Summarv of the _n ention We have found an improved solid hea~y duty laundry detergent composition having a zero phosphorus con~ent that effectively conditions ser~ice water. The detersent composition comprises a source of alkalinity, a water-conditioning copolymer of acrylic acid and itzconic acid, and a second vinyl pol~mer comprising polyacrylic acid, polyma1eic acid and copolymers of acrylic acid and maleic acid and at least one nonionic detergent surfactant.
We have also found a method or making a solid heavy duty laundry detergent having a zero phosphorus content in lS which said method avoids gel problems during manufacture oE
the detergen~.
The detergent composition of the invention provides water conditioning and detergency benefits substantially comparable to phosphorus-containing detergents wlthout the accompanying environmental harm. The invention exhibits a level of sequestrant action substantially equivalent to condensed phosphate containing `d~é~ergentS. This lével of~
sequestrant action provides an effective ~etergent without the undesirable side effects of phosphate~ sequestering 25 ~agents.
Detailed Descri~tion of the Invention The improved solid heavy duty laundry detergent composition having a zero phosphorus content comprises a source of alkalinity, a blend of two water conditioning builder polymers and a nonionic surfactant. The builder polymer components of the detergent composition~comDrise a blend of two vinyl polymers having pendant carboxyl groups.
The first builder polymer comprises any vinyl polymer, with pendent carboxyl groups, having hardness sequestering ; 35 properties. The second~ builder polymer is a different polymer than the first and comprises a copolymer of acrylic acid and itaconic acid. The builder components are , , ~ ~ 3 2 ~
- 3 - :.
combinéd with a source of alkalinity and at least one nonionic detergent surfactant, preferably a mixed nonionic ~ ;
surfactant system to form the detergent composition.
The vinyl polymer having pendant carboxyl groups is a builder or water-conditioning agent which can act to condition wash solutions under end-use conditions and to reduce the harmful effects of water hardness. This polymer has an average molecular weight of between about 500 and about 15,000 and has in its molecular structure the groups derived from an alpha beta unsaturated mono- or dicarboxylic acid or anhydride:
~C I - Ctn H COOH
optionally together with the group derived from a co-monomer:
3 1 :
tCI ctm in which Rl is hydrogen or an alkyl group having 1 to 4 :~
carbon atoms; R2 is hydrogen, an alkyl or alkoxy group having from 1 to 4 carbon atoms, or a carboxylic acid group; R3 is hydrogen or an alkyl group having l to 4 carbon atoms; and R4 is a hydroxyl group, an alkyl group having l to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aldehyde group, or a carboxylic acid group.
Specific examples of such a vinyl polymer useful in the invention include a water-soluble acrylic polymer including polyacrylic acid, polymethacrylic acid, acrylic acid-methacrylic acid copolymers, hydrolyzed 1 3 2 ~
polyacrylamide, hydrolyzed polymethacrylamide, hydrolyzed acrylamidemethacrylamide copolymers, hydrolyzed polyacrylonitrile, hydrolyzed polymethacrylonitrile, hydrolyzed acrylonitrile methacrylonitrile copolymers, or mixtures thereof. Water-soluble salts or partial salts of these polymers, such as the respective alkali metal (e.g., sodium, potassium) or ammonium salts can also be used. The weight average molecular weight of the polymers is from about 500 to about 15,000 and is preferably within the lQ range of from about 750 to about I0,000. Preferred polymers include polyacrylic acid, the partial sodium salt of polyacrylic acid or sodium polyacrylate having molecular weights of about 1,000 to about 6,000. These polymers are commercially available and methods for their preparation are well-known in the art.
For example, commercially-available water-conditioning polyacrylate solutions useful in the present invention include the sodium polyacrylate solution, Colloid~ 207 (Colloids, Inc., Newark, New Jersey); the polyacrylate acid solution, Aquatreat~ Ar-602-A ~Alco Chemical Corp., Chattanooga, Tennessee); the polyacrylic acid solutions (50-65~ solids) and the sodium polyacrylate powders (M.W.
LAUNr)RY DET~RGENT COI~OSITION
~ield of the _nvention The invention pertalns to a solid heavy duty laundry detergent compGsition having a zero phos~norus content.
More specifically, the in-~ention pertains to a novel heavy duty detergent compositlon that can so~ten (i.e., treat divalent or trivalent hardness lons in) servlce water containing the detersent composition either be.ore or during deter~ent action.
Much attention has been given in recent years to the components o. detergen~s that treat or reduce the harmful effects of water hardness on cleaning compositions and processes. Hardness ions are typically undesirable in conjunction with washing deter~ents since they interfere with the soil removal .~echanism of detergents. Such ions typically comorise metal ions such as calcium, magnesium, iron, manganese, and other typically divalent or trivalent metal cations de?ending on the source of service water used in the washing environment.
In recent years, the use of e'fective concentrations of complex phosphates such as sodium tripolyphosphate, and other sequestrants, in detergents as water softening agents has come under increasing attack due to environmental concerns. PhosDhates have been identified as contributing to excess water eutrophication, a process o.' algae overgrowth in environmental waters. .~any state governments have found it desira~le to cause detergent makers to replace phos~ha~es with components that do not sti~ulate algae growth. Therefore, some states have legislated that detergent compositions have a zero ~hosphorus content.
Currently, there are no phosphorus free heavy duty solid laundry detergent products available in the United States.
Accordingly, a substantial need exists to provide a solid heavy duty laundry detergent without intentionally .
1329~01 added phosphates or phosphorus that has the detergency and water conditioning benefits of phosphorus-containing detergents without the assoclated environmental harm.
Summarv of the _n ention We have found an improved solid hea~y duty laundry detergent composition having a zero phosphorus con~ent that effectively conditions ser~ice water. The detersent composition comprises a source of alkalinity, a water-conditioning copolymer of acrylic acid and itzconic acid, and a second vinyl pol~mer comprising polyacrylic acid, polyma1eic acid and copolymers of acrylic acid and maleic acid and at least one nonionic detergent surfactant.
We have also found a method or making a solid heavy duty laundry detergent having a zero phosphorus content in lS which said method avoids gel problems during manufacture oE
the detergen~.
The detergent composition of the invention provides water conditioning and detergency benefits substantially comparable to phosphorus-containing detergents wlthout the accompanying environmental harm. The invention exhibits a level of sequestrant action substantially equivalent to condensed phosphate containing `d~é~ergentS. This lével of~
sequestrant action provides an effective ~etergent without the undesirable side effects of phosphate~ sequestering 25 ~agents.
Detailed Descri~tion of the Invention The improved solid heavy duty laundry detergent composition having a zero phosphorus content comprises a source of alkalinity, a blend of two water conditioning builder polymers and a nonionic surfactant. The builder polymer components of the detergent composition~comDrise a blend of two vinyl polymers having pendant carboxyl groups.
The first builder polymer comprises any vinyl polymer, with pendent carboxyl groups, having hardness sequestering ; 35 properties. The second~ builder polymer is a different polymer than the first and comprises a copolymer of acrylic acid and itaconic acid. The builder components are , , ~ ~ 3 2 ~
- 3 - :.
combinéd with a source of alkalinity and at least one nonionic detergent surfactant, preferably a mixed nonionic ~ ;
surfactant system to form the detergent composition.
The vinyl polymer having pendant carboxyl groups is a builder or water-conditioning agent which can act to condition wash solutions under end-use conditions and to reduce the harmful effects of water hardness. This polymer has an average molecular weight of between about 500 and about 15,000 and has in its molecular structure the groups derived from an alpha beta unsaturated mono- or dicarboxylic acid or anhydride:
~C I - Ctn H COOH
optionally together with the group derived from a co-monomer:
3 1 :
tCI ctm in which Rl is hydrogen or an alkyl group having 1 to 4 :~
carbon atoms; R2 is hydrogen, an alkyl or alkoxy group having from 1 to 4 carbon atoms, or a carboxylic acid group; R3 is hydrogen or an alkyl group having l to 4 carbon atoms; and R4 is a hydroxyl group, an alkyl group having l to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aldehyde group, or a carboxylic acid group.
Specific examples of such a vinyl polymer useful in the invention include a water-soluble acrylic polymer including polyacrylic acid, polymethacrylic acid, acrylic acid-methacrylic acid copolymers, hydrolyzed 1 3 2 ~
polyacrylamide, hydrolyzed polymethacrylamide, hydrolyzed acrylamidemethacrylamide copolymers, hydrolyzed polyacrylonitrile, hydrolyzed polymethacrylonitrile, hydrolyzed acrylonitrile methacrylonitrile copolymers, or mixtures thereof. Water-soluble salts or partial salts of these polymers, such as the respective alkali metal (e.g., sodium, potassium) or ammonium salts can also be used. The weight average molecular weight of the polymers is from about 500 to about 15,000 and is preferably within the lQ range of from about 750 to about I0,000. Preferred polymers include polyacrylic acid, the partial sodium salt of polyacrylic acid or sodium polyacrylate having molecular weights of about 1,000 to about 6,000. These polymers are commercially available and methods for their preparation are well-known in the art.
For example, commercially-available water-conditioning polyacrylate solutions useful in the present invention include the sodium polyacrylate solution, Colloid~ 207 (Colloids, Inc., Newark, New Jersey); the polyacrylate acid solution, Aquatreat~ Ar-602-A ~Alco Chemical Corp., Chattanooga, Tennessee); the polyacrylic acid solutions (50-65~ solids) and the sodium polyacrylate powders (M.W.
2,100 and 6,000) and solutions (45% solids) available as the Goodright~ K-700 series from B. F. Goodrich Co.; and the sodium or partial sodium salts of polyacryllc acid solutions (M.W. 1,000-4,500), available as the ACRYSOL~
series from Rohm and Haas. A specifically preferred polyacrylic acid useful in the invention is neutralized polyacrylic acid under the trade name Goodright K-7058N
having a molecular weight of about 4500.
The second polymer is different than the first. We have found that the combination of any generic carboxylate polymer with the second itaconic acid/acrylic copolymer surprisingly produces a water conditioning properly substantially equivalent to condensed phosphate sequestrants. The second polymer comprises itaconic acid and a carboxyl containing acrylic monomer. It has been :
found that this ~ar~ cular copolymer is an e:ccellent calcium ion se~uestering a~ent.
Itaconic acid has the ollowing che~ical structure:
S C.~ 1 2 CH2 -co2~q and acrylic acid has the rollowing cnemical structure:
O
:: " : ::
~ Cii~2=C~-C-OH
~ , The itaconic acid - acrylic acid co~olymer e.~ployed in the composition of the invention can have a weight average molecular ~eight of about 1,500 to 100,000, preferably about 12,000 to ~0,0~0. This copolymer can be pcepared by conventional methods o~ polymerization well-known to those skilled in the art. The weight ratio of itaconic acid to acrylic acid is from about 0.5 to 2.0:1, preferably about 1 to 2~
The source~ or alkalinity is selected from the group consisting o alkali metal hydroxides, such as sodium hydroxide, potassium hydroxide, or mixtures of each thereof. ~Alkali metaL siliaates, such ;as~ sodium metasilicate, may also be used. The ~preferred source of alkalinity, whiah is the mos~ cost effective, is commercially aYailable sodium ~ hydroxide, which can be obtained in aqu~eous solutions at a concentration oE about 50 wt-% and in a~variet~ of solid~forms of~varying particle ;
sizes. Thel sodium hydroxide can be emplo~ed in the invention in either liquid or~solid form (powdered, beads, or pellets), or a mixture~of both.
3S Other sources of alkalinity useful include,~but are not limited to, the following~i alkali metal carbonates, ; alkali metal blcarbonates, alkali metal sesquicarbonates, ~ alkali metal borates, and alkali me.al silicate. The : : :
~: :
: ~ ' .
: -3 2 ~
carbonate and borate forms are typically used in place of alkali metal hydroxide when a lower p~ is desired.
Silicates (Na2O:SiO2 compounds) which are typically a reaction product between sodium hydroxide and silica, have a variety of Na2O:SiO2 reaction molar ratios. Silicates are primarily used as alkalies and as builders in both warewashing and laundry formulations.
A nonionic surfactant may be employed, either alone or in combination with other nonionic surfactants. A
surfactant is a chemical compound with a hydrophobe/hydrophile balance suitable as a wetting agent, defoamer and emulsifier. Typically, surfactants are nonionic organic surface-active polymers having hydrophobic groups, blocks or chains and hydrophilic ester groups, blocks, units or chains. The hydrophobicity can be provided by an oleophilic portion of the molecule, such as an aromatic alkyl or aralkyl group, an oxypropylene unit or oxypropylene chain, or other oxyalkylene functional groups other than oxyethylene, e.g. tetramethylene oxide. The hydrophilicity can be provided with oxyethylene units, chains or blocks and/or ester groups (e.g. organo-phosphate esters), salt-type groups, or salt-forming groups. This class of synthetic detergents may be produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophilic group can be readily adjusted to yield a water soluble or dispersible compound having the desired degree of balance between hydrophilic and hydrophobic elements.
Nonionic synthetic surfactants suitable in the present invention include the polyethylene oxide condensates of alkyl phenols, the products derived from the condensation of ethylene oxide with the reaction product of propylene oxide and ethylene diamine, the condensation product of aliphatic fatty alcohols with ethylene oxide as well as ~ ~L 3 2 ~
amine oxides and phosphine oxides, and the products derived from the condensation of ethylene oxide with the reaction product of propylene oxide and propylene glycol.
Preferred nonionic surfactants are the ethoxylated S alkylphenols, such as nonylphenol ethoxylate. It has been found that a blend of a first nonylphenol ethoxylate (NPE) having a mole ratio of ethylene-oxide to nonylphenol of 9 -lO:l and a second nonylphenol ethoxylate (NPE) having a mole ratio of ethylene-oxide to nonylphenol of 6 - 7:1 provides improved detergent action and allows for a broader range of cleaning temperature (120 F.-160 F.).
This mixed nonionic surfactant system is particularly useful in the invention, with the first NPE and the second NPE having a weight average molecular weight of about 600 to 700 and 450 to 550, respectively.
By the term "zero phosphorus" we mean no intentionally added phosphorus containing substrates such as condensed phosphates. Minute concentrations of phosphates may be present as a result of impurities or other non-inte~tional additions~
The detergent composition of the invention can be made in any physical form, such as a cast solid, powder, granulates, pellets, or a liquid slurry. The cast solid is formed by pouring the detergent in its molten state into a cast or mold, and allowed to solidify. The detergent composition also contains soft water and can have various additives such as fabric brighteners, fabric softeners, dyes, and fragrances.
Thus, the laundry detergent composition of the present invention comprises about 10 - 50%, preferably about 35 -45%, of a source of alkalinity; about~ 5 - 30%, preferably about 15 - 25%, of a water-conditioning vinyl polymer with pendant carboxyl groups, having a molecular weight of about 500-15lO00, preferably about 4,000 - 6,000; about 2 - 20~, preferably about 5 - 10%, of a water-conditioning copolymer of acrylic acid and itaconic acid, having a molecular weight of about 500 - 15,000, pre~erably about 10,000 -11 3 ~
12,000; and about 8 - 18% of at least one nonionic surfactant, preferably about 0 - 15% of a mixed nonionic surfactant system having a molecular weight of about 40Q - 900, preferably about 450 - 700.
~ preferred source of alkalinity would be about 20 -40% of sodium hydroxide beads and about 20 - 35% of 50 wt-~
aqueous sodium hydroxide. The preferred vinyl polymer is neutralized polyacrylic acid which avoids gelling problems during manufacture of the detergent. The term "neutralized" means that the pH of the polyacrylic acid is about 5.0 - lOØ The detergent composition further comprises about 25 - 30~ of water.
The present detergent composition may be readily prepared by charging an aqueous solution of an alkali metal hydroxide into a stainless steel mixing vessel having a recirculation line and pump, then agitating and heating the solution. The nonionic surfactant is then added into the vessel, followed by the copolymer of acrylic acid and itaconic acid. Fabric softener, dye, and soft water are added next. Beads of alkali metal hydroxide are next added, followed by a vinyl po~ymer such as polyacrylic acid. After thoroughly mixing and cooling, the composition is passed through a screen and packaged.
The present invention is particularly suited for use in heavy duty institutional laundering. The term "heavy duty" refers to the ability of a detergent composition to clean various articles such as sheets, pillowcases, blankets, towels, etc. The service water employed in the laundering process dissolves the detergent composition to form an aqueous wash solution that is at a temperature of about 100 - 160 F. The wash solution is then contacted with a soiled article for a period of time effective to clean the soiled article.
The invention will be further described by reference to the following detailed examples and test results which include a best mode.
Example I
~ 132~01 g A stainless steel mixing vessel was charged with 111.2 g of 50 wt-~ aqueous sodium hydroxide, agitation W2S
started and the batch was heated to 130-140 F. The nonylphenol ethoxylates (~PE 9.5, 36.0 g and ~PE 6.5 19.2 g] were then added to the vessel and batch temperature was maintained. The coDolymer of acryll acld and itaconic acid ~28.0 g) was ne~t added slowly to ~aintain the temperature in the 170-190 F. range. A fabric brightener rluoresing agent (TinGpal*C3S 0.3 g) was ne.~t added slowly to insure maxlmum dlspersion. A dye (Sanogran ~lue 2GLS, .0048 g) was pre-~et wlth a small a~ount of soft water (part of a 5.2952 g portion of water) before being added to ~the vessel. The remaining portlon of soft water was then charged into the vessel. Sodium hydroxide beads (120 g) were next added slowly to the vessel and the batch temperature was maintained between 155-165 P. Neutralized polyacrylic acid (180 g~ was next charged into the vessel slowly to prevent gelling. The batch was allowed to mix from 15-20 minutes and then cooled to 130-140 F. for packaging.
The final weight-~ of the active ingredients of Example I are summarized in Table I.
Examples II-VII
Table I summarizes the composition of additional soIid detergents that were prepared by the method of the lnvention.
`: : :
::
~ .
~ *Trade-mark : .
:
' ~ ` :
' -- :L 3 ~
00 N .
H ID n ~ r~ .
~ CO ~ ' ~ o O O
I ~ I o I~'1 ~
0 ~ Or~ I O 1 N
t O ~ O O O O
r Pd~ I j I OLt1 ¦
H¦ O ~ ~
r c O O =~ O I I ~
)_ N ~D N ~ 7 ~ ~D I l x L~
~ I a~
cr~ I
o u ~ à m u U M ; ~ , s ~ :
~32~
While the invention has been described and fully explained in the detailed description of the specification and preferred embodiments, many embodiments of the 5 invention can be made without departing from the spirit and ~ :
scope of the invention.
series from Rohm and Haas. A specifically preferred polyacrylic acid useful in the invention is neutralized polyacrylic acid under the trade name Goodright K-7058N
having a molecular weight of about 4500.
The second polymer is different than the first. We have found that the combination of any generic carboxylate polymer with the second itaconic acid/acrylic copolymer surprisingly produces a water conditioning properly substantially equivalent to condensed phosphate sequestrants. The second polymer comprises itaconic acid and a carboxyl containing acrylic monomer. It has been :
found that this ~ar~ cular copolymer is an e:ccellent calcium ion se~uestering a~ent.
Itaconic acid has the ollowing che~ical structure:
S C.~ 1 2 CH2 -co2~q and acrylic acid has the rollowing cnemical structure:
O
:: " : ::
~ Cii~2=C~-C-OH
~ , The itaconic acid - acrylic acid co~olymer e.~ployed in the composition of the invention can have a weight average molecular ~eight of about 1,500 to 100,000, preferably about 12,000 to ~0,0~0. This copolymer can be pcepared by conventional methods o~ polymerization well-known to those skilled in the art. The weight ratio of itaconic acid to acrylic acid is from about 0.5 to 2.0:1, preferably about 1 to 2~
The source~ or alkalinity is selected from the group consisting o alkali metal hydroxides, such as sodium hydroxide, potassium hydroxide, or mixtures of each thereof. ~Alkali metaL siliaates, such ;as~ sodium metasilicate, may also be used. The ~preferred source of alkalinity, whiah is the mos~ cost effective, is commercially aYailable sodium ~ hydroxide, which can be obtained in aqu~eous solutions at a concentration oE about 50 wt-% and in a~variet~ of solid~forms of~varying particle ;
sizes. Thel sodium hydroxide can be emplo~ed in the invention in either liquid or~solid form (powdered, beads, or pellets), or a mixture~of both.
3S Other sources of alkalinity useful include,~but are not limited to, the following~i alkali metal carbonates, ; alkali metal blcarbonates, alkali metal sesquicarbonates, ~ alkali metal borates, and alkali me.al silicate. The : : :
~: :
: ~ ' .
: -3 2 ~
carbonate and borate forms are typically used in place of alkali metal hydroxide when a lower p~ is desired.
Silicates (Na2O:SiO2 compounds) which are typically a reaction product between sodium hydroxide and silica, have a variety of Na2O:SiO2 reaction molar ratios. Silicates are primarily used as alkalies and as builders in both warewashing and laundry formulations.
A nonionic surfactant may be employed, either alone or in combination with other nonionic surfactants. A
surfactant is a chemical compound with a hydrophobe/hydrophile balance suitable as a wetting agent, defoamer and emulsifier. Typically, surfactants are nonionic organic surface-active polymers having hydrophobic groups, blocks or chains and hydrophilic ester groups, blocks, units or chains. The hydrophobicity can be provided by an oleophilic portion of the molecule, such as an aromatic alkyl or aralkyl group, an oxypropylene unit or oxypropylene chain, or other oxyalkylene functional groups other than oxyethylene, e.g. tetramethylene oxide. The hydrophilicity can be provided with oxyethylene units, chains or blocks and/or ester groups (e.g. organo-phosphate esters), salt-type groups, or salt-forming groups. This class of synthetic detergents may be produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophilic group can be readily adjusted to yield a water soluble or dispersible compound having the desired degree of balance between hydrophilic and hydrophobic elements.
Nonionic synthetic surfactants suitable in the present invention include the polyethylene oxide condensates of alkyl phenols, the products derived from the condensation of ethylene oxide with the reaction product of propylene oxide and ethylene diamine, the condensation product of aliphatic fatty alcohols with ethylene oxide as well as ~ ~L 3 2 ~
amine oxides and phosphine oxides, and the products derived from the condensation of ethylene oxide with the reaction product of propylene oxide and propylene glycol.
Preferred nonionic surfactants are the ethoxylated S alkylphenols, such as nonylphenol ethoxylate. It has been found that a blend of a first nonylphenol ethoxylate (NPE) having a mole ratio of ethylene-oxide to nonylphenol of 9 -lO:l and a second nonylphenol ethoxylate (NPE) having a mole ratio of ethylene-oxide to nonylphenol of 6 - 7:1 provides improved detergent action and allows for a broader range of cleaning temperature (120 F.-160 F.).
This mixed nonionic surfactant system is particularly useful in the invention, with the first NPE and the second NPE having a weight average molecular weight of about 600 to 700 and 450 to 550, respectively.
By the term "zero phosphorus" we mean no intentionally added phosphorus containing substrates such as condensed phosphates. Minute concentrations of phosphates may be present as a result of impurities or other non-inte~tional additions~
The detergent composition of the invention can be made in any physical form, such as a cast solid, powder, granulates, pellets, or a liquid slurry. The cast solid is formed by pouring the detergent in its molten state into a cast or mold, and allowed to solidify. The detergent composition also contains soft water and can have various additives such as fabric brighteners, fabric softeners, dyes, and fragrances.
Thus, the laundry detergent composition of the present invention comprises about 10 - 50%, preferably about 35 -45%, of a source of alkalinity; about~ 5 - 30%, preferably about 15 - 25%, of a water-conditioning vinyl polymer with pendant carboxyl groups, having a molecular weight of about 500-15lO00, preferably about 4,000 - 6,000; about 2 - 20~, preferably about 5 - 10%, of a water-conditioning copolymer of acrylic acid and itaconic acid, having a molecular weight of about 500 - 15,000, pre~erably about 10,000 -11 3 ~
12,000; and about 8 - 18% of at least one nonionic surfactant, preferably about 0 - 15% of a mixed nonionic surfactant system having a molecular weight of about 40Q - 900, preferably about 450 - 700.
~ preferred source of alkalinity would be about 20 -40% of sodium hydroxide beads and about 20 - 35% of 50 wt-~
aqueous sodium hydroxide. The preferred vinyl polymer is neutralized polyacrylic acid which avoids gelling problems during manufacture of the detergent. The term "neutralized" means that the pH of the polyacrylic acid is about 5.0 - lOØ The detergent composition further comprises about 25 - 30~ of water.
The present detergent composition may be readily prepared by charging an aqueous solution of an alkali metal hydroxide into a stainless steel mixing vessel having a recirculation line and pump, then agitating and heating the solution. The nonionic surfactant is then added into the vessel, followed by the copolymer of acrylic acid and itaconic acid. Fabric softener, dye, and soft water are added next. Beads of alkali metal hydroxide are next added, followed by a vinyl po~ymer such as polyacrylic acid. After thoroughly mixing and cooling, the composition is passed through a screen and packaged.
The present invention is particularly suited for use in heavy duty institutional laundering. The term "heavy duty" refers to the ability of a detergent composition to clean various articles such as sheets, pillowcases, blankets, towels, etc. The service water employed in the laundering process dissolves the detergent composition to form an aqueous wash solution that is at a temperature of about 100 - 160 F. The wash solution is then contacted with a soiled article for a period of time effective to clean the soiled article.
The invention will be further described by reference to the following detailed examples and test results which include a best mode.
Example I
~ 132~01 g A stainless steel mixing vessel was charged with 111.2 g of 50 wt-~ aqueous sodium hydroxide, agitation W2S
started and the batch was heated to 130-140 F. The nonylphenol ethoxylates (~PE 9.5, 36.0 g and ~PE 6.5 19.2 g] were then added to the vessel and batch temperature was maintained. The coDolymer of acryll acld and itaconic acid ~28.0 g) was ne~t added slowly to ~aintain the temperature in the 170-190 F. range. A fabric brightener rluoresing agent (TinGpal*C3S 0.3 g) was ne.~t added slowly to insure maxlmum dlspersion. A dye (Sanogran ~lue 2GLS, .0048 g) was pre-~et wlth a small a~ount of soft water (part of a 5.2952 g portion of water) before being added to ~the vessel. The remaining portlon of soft water was then charged into the vessel. Sodium hydroxide beads (120 g) were next added slowly to the vessel and the batch temperature was maintained between 155-165 P. Neutralized polyacrylic acid (180 g~ was next charged into the vessel slowly to prevent gelling. The batch was allowed to mix from 15-20 minutes and then cooled to 130-140 F. for packaging.
The final weight-~ of the active ingredients of Example I are summarized in Table I.
Examples II-VII
Table I summarizes the composition of additional soIid detergents that were prepared by the method of the lnvention.
`: : :
::
~ .
~ *Trade-mark : .
:
' ~ ` :
' -- :L 3 ~
00 N .
H ID n ~ r~ .
~ CO ~ ' ~ o O O
I ~ I o I~'1 ~
0 ~ Or~ I O 1 N
t O ~ O O O O
r Pd~ I j I OLt1 ¦
H¦ O ~ ~
r c O O =~ O I I ~
)_ N ~D N ~ 7 ~ ~D I l x L~
~ I a~
cr~ I
o u ~ à m u U M ; ~ , s ~ :
~32~
While the invention has been described and fully explained in the detailed description of the specification and preferred embodiments, many embodiments of the 5 invention can be made without departing from the spirit and ~ :
scope of the invention.
Claims (34)
1. A solid laundry detergent composition for use in heavy duty institutional laundering that can remove divalent or trivalent hardness ions from service water, comprising:
a) about 10 - 50% of a source of alkalinity;
b) about 5 - 30% of a water-conditioning vinyl polymer with pendant carboxyl groups, having a molecular weight of about 500-15,000;
c) about 2 - 20% of a water conditioning copolymer of acrylic acid and itaconic acid having a molecular weight of about 500 -15,000; and d) about 8 - 18% of at least one nonionic surfactant having a molecular weight or about 400 - 900.
a) about 10 - 50% of a source of alkalinity;
b) about 5 - 30% of a water-conditioning vinyl polymer with pendant carboxyl groups, having a molecular weight of about 500-15,000;
c) about 2 - 20% of a water conditioning copolymer of acrylic acid and itaconic acid having a molecular weight of about 500 -15,000; and d) about 8 - 18% of at least one nonionic surfactant having a molecular weight or about 400 - 900.
2. The detergent composition of claim 1 wherein said composition is in cast solid, powder, pellets, or granulated form.
3. The detergent composition of claim 1 wherein said source of alkalinity comprises alkali metal hydroxides or alkali metal silicates.
4. The detergent composition of claim 3 wherein said alkali metal hydroxide comprises sodium hydroxide, potassium hydroxide, or mixtures thereof.
5. The detergent composition of claim 3 wherein said alkali metal silicate comprises sodium metasilicate.
6. The detergent composition of claim 4 wherein said sodium hydroxide comprises about 20 - 40% of sodium hydroxide beads and 20 - 35% or 0.50 wt-% aqueous sodium hydroxide.
7. The detergent composition of claim 1 wherein said vinyl polymer comprises an acrylic polymer.
8. The detergent composition of claim 7 wherein said acrylic polymer comprises polyacrylic acid, the partial sodium salt of polyacrylic acid, sodium polyacrylate, or mixtures thereof, having a molecular weight of about 750-10,000.
9. The detergent composition of claim 8 wherein said polyacrylic acid is neutralized.
10. The detergent composition of claim 1 wherein said nonionic surfactant comprises a blend of a first nonylphenol ethoxylate having a molecular weight or about 450 - 500 and a second nonylphenol ethoxylate having a molecular weight of about 600 - 700.
11. The detergent composition of claim 1 wherein said composition has a zero phosphorus content.
12. The detergent composition or claim 1 wherein the vinyl polymer is a salt or partial salt or the vinyl polymer.
13. A solid laundry detergent composition having a zero phosphorus content that can remove divalent or trivalent hardness ions from service water suitable for use in heavy duty laundering comprising:
a) about 10 - 50% of an alkali metal hydroxide comprising sodium hydroxide, potassium hydroxide, or mixtures thereof;
b) about 5 - 30% of an acrylic polymer comprising polyacrylic acid, the partial sodium salt of polyacrylic acid or sodium polyacrylate having a molecular weight of about 1,000-6,000.
c) about 2 - 20% or a water conditioning copolymer comprising acrylic acid and itaconic acid, having a molecular weight of about 500 - 15,000;
d) about 8 - 18% of a mixed nonionic surfactant system comprising a first and second nonylphenol ethoxylate having weight average molecular weights of about 450 - 500 and 600 - 700 respectively.
a) about 10 - 50% of an alkali metal hydroxide comprising sodium hydroxide, potassium hydroxide, or mixtures thereof;
b) about 5 - 30% of an acrylic polymer comprising polyacrylic acid, the partial sodium salt of polyacrylic acid or sodium polyacrylate having a molecular weight of about 1,000-6,000.
c) about 2 - 20% or a water conditioning copolymer comprising acrylic acid and itaconic acid, having a molecular weight of about 500 - 15,000;
d) about 8 - 18% of a mixed nonionic surfactant system comprising a first and second nonylphenol ethoxylate having weight average molecular weights of about 450 - 500 and 600 - 700 respectively.
14. A process for cleaning a soiled article using a solid heavy duty laundry detergent composition that can condition service water by removing divalent or trivalent hardness ions comprising:
a) dissolving in water an effective amount of said detergent composition, thereby forming an aqueous wash solution, said detergent composition comprising:
i) about 10 - 50% of a source of alkalinity;
ii) about 5 - 30% of a water-conditioning vinyl polymer with pendant carboxyl groups, having a molecular weight of about 500 -
a) dissolving in water an effective amount of said detergent composition, thereby forming an aqueous wash solution, said detergent composition comprising:
i) about 10 - 50% of a source of alkalinity;
ii) about 5 - 30% of a water-conditioning vinyl polymer with pendant carboxyl groups, having a molecular weight of about 500 -
15,000;
iii) about 2 - 20% of a water-conditioning copolymer of acrylic acid and itaconic acid, having a molecular weight of about 500 -1,500; and iv) about 8 - 18% of at least one nonionic surfactant having a molecular weight of about 450 - 700; and b) contacting said aqueous wash solution of (a) with said soiled article for a period of time effective to clean said soiled article.
15. The process of claim 14 wherein said detergent composition is in cast solid, powder, granulated, or pellet form.
iii) about 2 - 20% of a water-conditioning copolymer of acrylic acid and itaconic acid, having a molecular weight of about 500 -1,500; and iv) about 8 - 18% of at least one nonionic surfactant having a molecular weight of about 450 - 700; and b) contacting said aqueous wash solution of (a) with said soiled article for a period of time effective to clean said soiled article.
15. The process of claim 14 wherein said detergent composition is in cast solid, powder, granulated, or pellet form.
16. The process of claim 14 wherein said source of alkalinity comprises alkali metal hydroxides or alkali metal silicates.
17. The process of claim 16 wherein said alkali metal hydroxides comprise sodium hydroxide, potassium hydroxide, or mixtures thereof.
18. The process of claim 16 wherein said alkali metal silicates comprise sodium metasilicate.
19. The process of claim 17 wherein said sodium hydroxide comprises about 20 - 40% of sodium hydroxide beads and 20 - 35% of 0.50 wt-% aqueous sodium hydroxide.
20. The process of claim 14 wherein said vinyl polymer comprises an acrylic polymer.
21. The process of claim 20 wherein said acrylic polymer comprises polyacrylic acid, the partial sodium salt of polyacrylic acid, sodium polyacrylate, or mixtures thereof, having a molecular weight of about 750-10,000.
22. The process of claim 21 wherein said polyacrylic acid is neutralized.
23. The process of claim 14 wherein said nonionic surfactant comprises a blend of a first nonylphenol ethoxylate having a molecular weight of about 450 - 500 and a second nonylphenol ethoxylate having a molecular weight of about 600 - 700.
24. The process of claim 14 wherein said detergent composition has a zero phosphorus content.
25. The process of claim 14 wherein said aqueous wash solution is applied to said soiled article at about 100 -140° F.
26. The process of claim 14 wherein the vinyl polymer is a salt or partial salt of the vinyl polymer.
27. A method of preparing a heavy duty solid laundry detergent composition that can condition service water comprising:
a) charging about 10 - 50% of an alkali metal hydroxide into a mixing vessel;
b) adding about 5 - 30% of a water conditioning acrylic polymer having a molecular weight of about 750-10,000.
c) adding about 2 - 20% of a water-conditioning copolymer of acrylic acid and itaconic acid having a molecular weight of about 500 -15000; and d) adding about 8 - 18% of at least one nonionic surfactant having a molecular weight of about 450 - 700.
a) charging about 10 - 50% of an alkali metal hydroxide into a mixing vessel;
b) adding about 5 - 30% of a water conditioning acrylic polymer having a molecular weight of about 750-10,000.
c) adding about 2 - 20% of a water-conditioning copolymer of acrylic acid and itaconic acid having a molecular weight of about 500 -15000; and d) adding about 8 - 18% of at least one nonionic surfactant having a molecular weight of about 450 - 700.
28. The method of claim 27 wherein said alkali metal hydroxide comprises sodium hydroxide, potassium hydroxide, or mixtures thereof.
29. The method of claim 28 wherein said sodium hydroxide comprises about 20 - 40% of sodium hydroxide beads and 20 - 35% of 0.50 wt-% aqueous sodium hydroxide.
30. The method of claim 27 wherein said acrylic polymer comprises polyacrylic acid, the partial sodium salt of polyacrylic acid, sodium polyacrylate, or mixtures thereof.
31. The method of claim 30 wherein said polyacrylic acid is neutralized.
32. The method of claim 27 wherein said detergent composition has a zero phosphorus content.
33. The method of claim 27 wherein said nonionic surfactant comprises a blend of a first nonylphenol ethoxylate having a molecular weight of about 450 - 500 and a second nonylphenol ethoxylate having a molecular weight of about 600 - 700.
34. The method of claim 27 wherein said detergent composition is in cast solid, powder, granulated, or pellet form.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US34598889A | 1989-05-02 | 1989-05-02 | |
US07/345,988 | 1989-05-02 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1329101C true CA1329101C (en) | 1994-05-03 |
Family
ID=23357445
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000609263A Expired - Fee Related CA1329101C (en) | 1989-05-02 | 1989-08-24 | Zero phosphorus heavy duty laundry detergent composition |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0470955B1 (en) |
JP (1) | JPH04505024A (en) |
AU (2) | AU4211889A (en) |
CA (1) | CA1329101C (en) |
DE (1) | DE68909615T2 (en) |
WO (1) | WO1990013622A1 (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5273675A (en) * | 1990-02-16 | 1993-12-28 | Rohm And Haas Company | Phosphate-free liquid cleaning compositions containing polymer |
US5308530A (en) * | 1990-11-21 | 1994-05-03 | Lever Brothers Company, Division Of Conopco, Inc. | Detergent compositions containing polycarboxylates and calcium-sensitive enzymes |
US5281351A (en) * | 1991-12-06 | 1994-01-25 | Lever Brothers Company, Division Of Conopco, Inc. | Processes for incorporating anti-scalants in powdered detergent compositions |
DE4239076A1 (en) * | 1992-11-20 | 1994-05-26 | Basf Ag | Mixtures of polymers of monoethylenically unsaturated dicarboxylic acids and polymers of ethylenically unsaturated monocarboxylic acids and / or polyaminocarboxylic acids and their use |
US5599784A (en) * | 1994-03-04 | 1997-02-04 | National Starch And Chemical Investment Holding Corporation | Aqueous lamellar detergent compositions with hydrophobically capped hydrophilic polymers |
US5489397A (en) * | 1994-03-04 | 1996-02-06 | National Starch And Chemical Investment Holding Corporation | Aqueous lamellar detergent compositions with hydrophobically terminated hydrophilic polymer |
US6194371B1 (en) | 1998-05-01 | 2001-02-27 | Ecolab Inc. | Stable alkaline emulsion cleaners |
GB2502558A (en) * | 2012-05-30 | 2013-12-04 | Reckitt Benckiser Nv | Water softening composition |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0124913B1 (en) * | 1983-04-08 | 1986-06-18 | THE PROCTER & GAMBLE COMPANY | Granular detergent compositions containing mixed polymer additive system |
DE3472571D1 (en) * | 1983-08-27 | 1988-08-11 | Procter & Gamble | Detergent compositions |
DE3412188A1 (en) * | 1984-04-02 | 1985-10-10 | Henkel KGaA, 4000 Düsseldorf | LAUNDRY DETERGENT |
-
1989
- 1989-08-23 AU AU42118/89A patent/AU4211889A/en not_active Abandoned
- 1989-08-23 WO PCT/US1989/003646 patent/WO1990013622A1/en active IP Right Grant
- 1989-08-23 JP JP1509361A patent/JPH04505024A/en active Pending
- 1989-08-23 EP EP89910259A patent/EP0470955B1/en not_active Expired - Lifetime
- 1989-08-23 DE DE89910259T patent/DE68909615T2/en not_active Expired - Fee Related
- 1989-08-24 CA CA000609263A patent/CA1329101C/en not_active Expired - Fee Related
-
1993
- 1993-10-29 AU AU50346/93A patent/AU666226B2/en not_active Ceased
Also Published As
Publication number | Publication date |
---|---|
AU4211889A (en) | 1990-11-29 |
EP0470955A1 (en) | 1992-02-19 |
DE68909615D1 (en) | 1993-11-04 |
AU666226B2 (en) | 1996-02-01 |
DE68909615T2 (en) | 1994-04-28 |
JPH04505024A (en) | 1992-09-03 |
AU5034693A (en) | 1994-01-13 |
EP0470955B1 (en) | 1993-09-29 |
WO1990013622A1 (en) | 1990-11-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0429307B1 (en) | Biodegradable, water-soluble graft copolymers, compositions containing such copolymers, and methods of use of such copolymers | |
AU702565B2 (en) | Improved proteolytic enzyme cleaner | |
US6172028B1 (en) | Detergent and tableware cleaner | |
EP0126551B1 (en) | Detergent compositions | |
CA1317186C (en) | Soil release composition | |
US4276205A (en) | Detergent compositions containing amine oxide and nonionic surfactants and polyethylene glycol | |
EP2773734B1 (en) | Sustainable laundry sour compositions with iron control | |
US5256327A (en) | Method of preparing a sequestering agent for a non-phosphate cleaning composition | |
NZ248033A (en) | Detergent compositions containing polysuccinimide | |
JPH04285627A (en) | Water-soluble or water-dispersible polyester, process for producing same and detergent containing same | |
US5066749A (en) | Hydrophobically-modified polycarboxylates and process for their preparation | |
CA1329101C (en) | Zero phosphorus heavy duty laundry detergent composition | |
US5574004A (en) | Carbonate built non-bleaching laundry detergent composition containing a polymeric polycarboxylate and a zinc salt | |
CA2871210A1 (en) | Formulations, their use as or for producing dishwashing detergents and their production | |
US4946627A (en) | Hydrophobically modified polycarboxylate polymers utilized as detergent builders | |
JPH05311194A (en) | Builder for detergent and detergent composition comprising the same | |
US6034045A (en) | Liquid laundry detergent composition containing a completely or partially neutralized carboxylic acid-containing polymer | |
EP0637627B1 (en) | Detergent formulations | |
US6180589B1 (en) | Polyether hydroxycarboxylate copolymers | |
US5575946A (en) | Water-softening compositions | |
CN109890947A (en) | The detergent composition of phosphate free and its application | |
KR20180094079A (en) | Concentrated liquid detergent containing anti-redeposition polymer | |
JPS6286098A (en) | Detergent builder and detergent composition containing the same | |
JPH11512139A (en) | Use of modified polyaspartic acid in detergents | |
WO2017167599A1 (en) | Concentrates, methods of manufacture, and uses |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
MKLA | Lapsed |