Process for preparing spray-dried laundry detergent particles
阅读说明：本技术 用于制备喷雾干燥的衣物洗涤剂颗粒的方法 (Process for preparing spray-dried laundry detergent particles ) 是由 乔斯·罗德尔·马比兰根·卡拉盖 H·H·坦塔维 于 2019-03-27 设计创作，主要内容包括：本发明涉及用于制备喷雾干燥的衣物洗涤剂颗粒的方法,其中所述方法包括使水不溶性硅酸盐与单体有机羧酸在含水混合物中接触的步骤,其中所述含水混合物具有4.2或更低的pH,其中所述含水混合物包含去污表面活性剂,其中所述含水混合物基本上不含碳酸盐,其中所述水不溶性硅酸盐与所述单体有机羧酸反应以形成二氧化硅,其中所述含水混合物被喷雾干燥以形成喷雾干燥的衣物洗涤剂颗粒,其中所述颗粒包含：去污表面活性剂、单体有机羧酸和二氧化硅,其中所述颗粒基本上不含碳酸盐。(The present invention relates to a process for the preparation of spray-dried laundry detergent particles, wherein the process comprises the step of contacting a water-insoluble silicate with a monomeric organic carboxylic acid in an aqueous mixture, wherein the aqueous mixture has a pH of 4.2 or lower, wherein the aqueous mixture comprises a detersive surfactant, wherein the aqueous mixture is substantially free of carbonate, wherein the water-insoluble silicate reacts with the monomeric organic carboxylic acid to form silica, wherein the aqueous mixture is spray-dried to form spray-dried laundry detergent particles, wherein the particles comprise: a detersive surfactant, a monomeric organic carboxylic acid and silica, wherein said particles are substantially carbonate-free.)
1. A process for the preparation of spray-dried laundry detergent particles,
wherein the process comprises the step of contacting a water-insoluble magnesium silicate salt with a monomeric organic carboxylic acid in an aqueous mixture,
wherein the aqueous mixture has a pH of 4.2 or less,
wherein the aqueous mixture comprises a detersive surfactant, wherein the aqueous mixture is substantially free of carbonate,
wherein the water-insoluble magnesium silicate salt reacts with the monomeric organic carboxylic acid to form silica,
wherein the aqueous mixture is spray dried to form spray dried laundry detergent particles,
wherein the particles comprise: detersive surfactant, monomeric organic carboxylic acid and silicon dioxide,
wherein the particles are substantially free of carbonate.
2. The method of claim 1, wherein the aqueous mixture has a pH of 3.5 or less.
3. The method of any preceding claim, wherein the particles have a pH of 6.0 or less when dissolved in deionized water at a concentration of 10 wt.% and a temperature of 25 ℃.
4. The method of any preceding claim, wherein the particles have a pH of 4.2 or less when dissolved in deionized water at a concentration of 10 wt.% and a temperature of 25 ℃.
5. The method of any preceding claim, wherein the particles have a pH of 3.5 or less when dissolved in deionized water at a concentration of 10 wt.% and a temperature of 20 ℃.
6. The method of any preceding claim, wherein the monomeric organic carboxylic acid is a monomeric organic polycarboxylic acid.
7. The method of claim 6, wherein the monomeric organic polycarboxylic acid is citric acid.
8. The method according to any preceding claims, wherein the detersive surfactant is alkyl benzene sulphonate.
9. The method of any one of the preceding claims, wherein the weight ratio of monomeric organic carboxylic acid to water-insoluble magnesium silicate present in the aqueous mixture is at least 1.6.
10. The method of any one of the preceding claims, wherein the aqueous mixture comprises magnesium sulfate, and wherein the particles comprise magnesium sulfate in amorphous form.
11. The method of any preceding claim, wherein the aqueous mixture comprises a carboxylate polymer, and wherein the particles comprise a carboxylate polymer.
12. The method of any one of the preceding claims, wherein the particles comprise:
(a)12 to 30 wt% of a detersive surfactant;
(b)4 to 10% by weight of a monomeric organic carboxylic acid;
(c)0.5 to 3% by weight of silica;
(d) optionally, 2 to 10 wt% magnesium sulfate;
(e) optionally, 0.5 to 5 wt% of a polymer;
(f) optionally, 35 to 80 weight% sodium sulfate; and
(g) optionally, 0 to 6 wt% water.
13. The method of any one of the preceding claims, wherein after the water-insoluble magnesium silicate salt has reacted with the monomeric organic carboxylic acid, the aqueous mixture comprises:
(a)20 to 40 wt% water;
(b)7.2 to 24 wt% of a detersive surfactant;
(c)2.4 to 8% by weight of a monomeric organic carboxylic acid;
(d)0.3 to 2.4% by weight of silica;
(e) optionally, 1.2 to 8 wt% magnesium sulfate;
(f) optionally, 0.3 to 4 weight percent of a polymer; and
(g) optionally, 21 to 64 wt% sodium sulfate.
14. A process according to any preceding claim, wherein the spray-dried laundry detergent particle has a bulk density of less than 550 g/l.
15. A process according to any preceding claim, wherein the spray-dried laundry detergent particles have a weight average particle size of from 300 microns to 600 microns.
Technical Field
The present invention relates to a process for the preparation of spray-dried laundry detergent particles. The particles are substantially carbonate free and have good particle characteristics such as good physical properties, cake strength, flowability, and good dispersion, dissolution and fabric retention properties (i.e., leave a low level of residue on washed fabrics after the washing process). The particles exhibit a low bulk density.
Background
In the laundry detergent manufacturing industry, a recent trend is to provide laundry detergent powders that, when dissolved in water, produce a wash liquid having a pH typically in the range of 7.0 to 9.0. Conventional laundry detergent powders today, when dissolved in water, provide a wash liquor with a pH in the range of 10.5 to 11.0, sometimes even higher. While high wash pH in these typical ranges provides good cleaning performance, it is difficult to provide fabric care benefits. In seeking to improve the fabric care performance of laundry detergent powders, detergent formulators are developing laundry powders that provide low pH wash liquor. Typically, this requires removal from the powder of large amounts of ingredients that provide alkalinity to the wash liquor. Such ingredients are typically carbonates, such as sodium carbonate. These ingredients are typically formulated into laundry powders not only to provide a wash liquor having a pH of about 10.5, but also to provide good physical characteristics to the laundry powder.
The base particles of laundry detergent powders are typically prepared by a spray-drying process. During the process, detergent ingredients such as detersive surfactant, polymer, filler salt (if used) are formed into an aqueous mixture (commonly referred to as a crutcher mixture) which is then spray-dried to form spray-dried laundry detergent particles. Such spray-dried particles may be used as a laundry detergent powder product or (and more generally) mixed with other ingredients such as bleach particles, enzyme particles, perfume, and sometimes additional surfactant particles and other dry add-on particles such as filler particles (such as sodium sulphate particles) to form a fully formulated laundry detergent powder.
The presence of carbonate in the spray-dried base granules not only provides alkalinity commonly used by detergent formulators to provide good cleaning (about 10.5), but also provides good physical characteristics to the spray-dried base detergent granules. Such physical properties include good cake strength and good flow.
However, recent advances in formulating laundry detergent powders, and therefore also spray-dried base detergent powders at lower pH, have resulted in the need to remove ingredients such as carbonates from the spray-dried base powders. This in turn leads to problems of poor physical properties in the spray dried granules being developed for these low pH laundry powder products.
Ingredients such as silica have been considered as alternatives to carbonates in spray dried granules. However, silicon dioxide is difficult to handle during the manufacturing process. The very low density and small particle size of the silica means that complex and elaborate processing equipment and controls will be required to dose the silica into the crutcher mixture prior to spray drying the mixture to form the spray-dried base particles. The behaviour of silica during its introduction into the crutcher mixture is often described as gas-like or smoke-like, thus creating a number of problems such as dusting and inaccurate dosing.
The present inventors have found that rather than incorporating silica as a starting material and attempting to dose it into a crutcher mixture, the silica can be formed in situ in the crutcher mixture by reaction of a water-insoluble silicate which forms silica in an aqueous environment under controlled pH conditions. To do this, the pH of the crutcher mixture must be carefully controlled in order to cause the reaction to occur.
Water-insoluble silicates are conventional detergent ingredients commonly found in laundry detergent powders. The method and manner of manufacture of incorporating water-insoluble silicates into crutcher mixtures is well recognized. However, the present inventors have found that instead of incorporating water-insoluble silicates into the spray-dried powder, water-insoluble silicates can be used as a matrix to form silica in situ during the spray-drying process. The water-insoluble silicate is converted to silica and the resulting spray-dried laundry particles are suitable not only for low pH laundry powders, but also for low built laundry powders. The resulting granules also have dispersion, dissolution of low built laundry detergent powders and good fabric residue property profile due to the conversion of the water insoluble silicate to silica during the manufacturing process.
The process provides a process for producing spray-dried granules that can be used to formulate low pH laundry powders that benefits from the presence of silica, such as good physical characteristics, without all the problems associated with attempting to dose silica directly into crutcher mixtures as a starting ingredient. In addition, the granules produced by the process also have good dispersion, dissolution and good fabric retention property profiles.
In addition, low pH laundry powders tend to have relatively high bulk densities. This tendency to produce spray-dried detergent base particles having a higher bulk density can cause problems when the detergent powder needs to meet certain (low) bulk density requirements that consumers prefer. On a commercial scale, this means that (high) bulk density problems can occur in spray-drying manufacturing equipment, and such increases in bulk density need to be controlled in order to offset the increase in bulk density. This in turn may lead to the need for complex air injection systems which are expensive and present their own set of problems which need to be addressed, or may lead to the need to reduce the production rate of spray-drying manufacturing equipment to ensure that the target low bulk density of the resulting spray-dried laundry powder is met.
The present inventors have found that the process of the present invention results in the formation of a spray-dried powder having a lower bulk density. The in situ formation of silica by the process of the present invention reduces the bulk density of the resulting powder. This overcomes the bulk density problem discussed above, provides a solution to the bulk density problem, and avoids the need to reduce the production rate of commercial spray-dried laundry detergent appliances, or the need to incorporate any complex density management system in commercial spray-dried laundry detergent appliances.
Disclosure of Invention
The present invention relates to a process for the preparation of spray-dried laundry detergent particles, wherein the process comprises the step of contacting a water-insoluble silicate with a monomeric organic carboxylic acid in an aqueous mixture, wherein the aqueous mixture has a pH of 4.2 or lower, wherein the aqueous mixture comprises a detersive surfactant, and wherein the aqueous mixture is substantially free of carbonate, wherein the water-insoluble silicate reacts with the monomeric organic carboxylic acid to form silica, wherein the aqueous mixture is spray-dried to form spray-dried laundry detergent particles, wherein the particles comprise: a detersive surfactant, a monomeric organic carboxylic acid and silica, and wherein the particles are substantially carbonate-free.
Detailed Description
Process for preparing spray-dried laundry detergent particles: a process for preparing spray-dried laundry detergent particles comprising the step of contacting a water-insoluble silicate with a monomeric organic carboxylic acid in an aqueous mixture, wherein the aqueous mixture has a pH of 4.2 or lower, wherein the aqueous mixture comprises a detersive surfactant, and wherein the aqueous mixture is substantially free of carbonate, wherein the water-insoluble silicate reacts with the monomeric organic carboxylic acid to form silica, wherein the aqueous mixture is spray-dried to form spray-dried laundry detergent particles, wherein the particles comprise: detersive surfactant, monomeric organic carboxylic acid and dioxideSilicon, and wherein the particles are substantially free of carbonate.
The steps of forming the aqueous mixture and spray drying the aqueous mixture are described in more detail below. The spray drying process may be carried out using any typical spray drying equipment. The apparatus generally includes a mixer, typically referred to as a crutcher mixture. It is not uncommon to use a second mixer or reservoir after the first mixer, with one common example being a drip can. Typically, pipes are used which are usually combined with one or more pumps to transfer the aqueous mixture from the mixer to the spray nozzles, where the aqueous mixture is then transferred through the nozzles into the spray drying tower. Typically, a first low pressure pump is used followed by a second high pressure pump to transfer the aqueous mixture through a conduit.
Forming an aqueous mixture: the aqueous mixture is typically formed by contacting a detersive surfactant, a monomeric organic carboxylic acid, a water-insoluble silicate and water, it being highly preferred that the detersive surfactant is present when the water-insoluble silicate is contacted with the monomeric organic carboxylic acid. The preferred order of addition is to contact the detersive surfactant with water, then with the monomeric carboxylic acid, and finally with the water-insoluble silicate. To produce a spray-dried laundry powder having a low bulk density, the pH of the aqueous mixture must be 4.2 or less. Preferably, the pH of the aqueous mixture is 3.5 or less. The water-insoluble silicate reacts with the monomeric organic carboxylic acid to form silica. It is also a preferred feature of the invention to control the weight ratio of monomeric organic carboxylic acid to water-insoluble silicate.
The aqueous mixture is substantially free of carbonate. By "substantially free" it is typically meant "not intentionally added". After the silica is formed, it may be useful to reintroduce some alkalinity into the aqueous mixture, depending on the desired pH of the wash liquor as required by the detergent formulator. However, large amounts of alkalinity chemicals, such as carbonates and/or additional silicates, are not used. In this regard, alkalinity agents such as NaOH are particularly useful. Typically, fully formulated laundry detergent powders that may comprise spray dried particles should be such that when dissolved with water at 20 ℃ and dissolved at a concentration of 1g/L in deionized water have a pH in the range of 7.0 to 9.5, preferably 7.5 to 9.0, or 7.5 to 8.5. This is considered to be the optimum pH of the low pH laundry detergent powder to provide good fabric care benefits while also providing good fabric cleaning performance. The process of the present invention allows the formation of spray dried particles with a low pH profile, which is typically well below this optimum pH of the final wash liquor.
Typically, the spray dried particles have a pH of 6.0 or less, or even 5.0 or less, or 4.2 or less, or even 3.5 or less, when dissolved in deionized water at a concentration of 1g/L and at a temperature of 20 ℃. This pH profile can still be used when formulating laundry detergent powders because the spray-dried particles can be combined with other ingredients to raise the pH of the wash liquor back to the ideal pH range described above (e.g. 7.0 to 9.5). For example, the introduction of sodium percarbonate bleach as a dry additive into laundry powder for use in combination with spray-dried base particles is one such source of alkalinity. Detergent formulators can take into account all such pH effects when formulating their desired laundry detergent powders.
Spray drying aqueous mixturesTypically, spray drying an aqueous mixture includes the step of diverting the aqueous mixture first through a first pump and then through a second pump through a conduit to a plurality of spray nozzles5To 1 × 106Pa, the second pump is typically a high pressure pump, such as can produce 2 × 106To 1 × 107Pa pressure the pressure in the conduit at the outlet of the first pump may be less than 1 × 106Pa. The aqueous detergent slurry is preferably transferred through a disintegrator, such as that provided by Hosakawa Micron. The shredder is typically positioned between the two pumps. The flow rate of the aqueous detergent slurry along the pipe is typically in the range of 800kg/h to more than 50,000 kg/h.
A suitable pressure spray nozzle is the spray system T4C8 nozzle, where multiple nozzles may be used at different heights within the tower. Preferably, the temperature of the aqueous detergent slurry is from 60 ℃ to 130 ℃. Suitable spray drying towers are concurrent or countercurrent spray drying towers, the latter of which can be operated as a cyclone tower. Preferably, the inlet air temperature of the spray drying tower is in the range of 220 ℃ to 350 ℃. Preferably, the temperature of the exhaust gas reaching the spray drying tower is in the range of 60 ℃ to 100 ℃. The spray-dried powder may be subjected to cooling, for example air-lift. Typically, the spray-dried powder is size-classified to remove oversize material (>1.8mm) to form a free-flowing spray-dried powder. Fine material (<0.15mm) was elutriated with exhaust gas in the spray drying tower and then collected in the post-tower dust control system.
Aqueous mixture: the aqueous mixture has a pH of 4.2 or less, preferably 3.5 or less. Preferably, the weight ratio of monomeric organic carboxylic acid to water-insoluble silicate present in the aqueous mixture is at least 1.0, preferably at least 1.2, or even at least 1.2, and most preferably at least 1.6. The excess of monomeric organic carboxylic acid relative to the water-insoluble silicate ensures good reaction kinetics for the formation of silica, and also maintains and enables good pH control of the aqueous mixture.
The aqueous mixture (which may also be referred to as a crutcher mixture) may also contain other detergent ingredients suitable for inclusion into spray-dried laundry detergent granules. Suitable ingredients are described in more detail below, but include polymers, chelating agents, hueing dyes, brighteners, colorants, and pigments. Preferably, the aqueous mixture comprises a carboxylate polymer.
After the water-insoluble silicate has been reacted with the monomeric organic carboxylic acid, the preferred chemical composition of the aqueous mixture is such that the aqueous mixture comprises: (a)20 to 40 wt% water; (b)7.2 to 24 wt% of a detersive surfactant; (c)2.4 to 8% by weight of a monomeric organic carboxylic acid; (d)0.3 to 2.4% by weight of silica; (e) optionally, 1.2 to 8 wt% magnesium sulfate; (f) optionally, 0.3 to 4 weight percent of a polymer; and (g) optionally, 21 to 64 wt% sodium sulfate.
Spray-dried laundry detergent particles: the particles comprise: detersive surfactant, monomeric organic carboxylic acid and silica. The particles are substantially free of carbonate. The particles may be substantially free of water-insoluble silicates. Other ingredients may be included in the particles, which are described in more detail below. Preferably, the particles comprise: (a)12 to 30 wt% of a detersive surfactant; (b)4 to 10% by weight of a monomeric organic carboxylic acid; (c)0.5 to 3% by weight of silica; (d) optionally, 2 to 10 wt% magnesium sulfate; (e) optionally, 0.5 to 5 wt% of a polymer; (f) optionally, 35 to 80 weight% sodium sulfate; and (g) optionally, 0 to 6 wt% water.
As described above, the particles may have a pH of 6.0 or less, or 5.0 or less, or 4.2 or less, or 3.5 or less when dissolved in deionized water at a concentration of 10 wt.% and at a temperature of 25 ℃. The particles may contain an alkalinity agent, a preferred alkalinity agent being NaOH.
The particles may comprise magnesium sulphate, preferably the particles comprise magnesium sulphate in amorphous form.
The spray dried particles typically have a bulk density of less than 550 g/l. The method of measuring bulk density is described in more detail below.
The spray dried particles typically have a weight average particle size of from 300 microns to 600 microns. The method of measuring the weight average particle size is described in more detail below.
Monomeric organic carboxylic acids: the monomeric organic carboxylic acid is preferably a monomeric organic polycarboxylic acid, most preferably citric acid. Suitable acids include:
formic acid, acetic acid, propionic acid, butyric acid, caprylic acid and lauric acid, stearic acid, linoleic acid and acrylic acid, methacrylic acid, chloroacetic acid, citric acid, lactic acid, glyoxylic acid, acetoacetic acid, oxalic acid, malonic acid, adipic acid and phenylacetic acid, benzoic acid, salicylic acid, glycine and alanine, valine, aspartic acid, glutamic acid, lysine and phenylalanine, nicotinic acid, picolinic acid, fumaric acid, lactic acid, benzoic acid, glutamic acid; succinic acid, glycolic acid. Preferably, the organic acid is selected from the group consisting of citric acid, malic acid, succinic acid, lactic acid, glycolic acid, fumaric acid, tartaric acid and formic acid, and mixtures thereof. More preferably, the acids are citric acid, lactic acid and tartaric acid. Most preferably citric acid.
Water-insoluble magnesium silicate salt: suitable water-insoluble silicates are water-insoluble magnesium silicates. A suitable magnesium silicate salt is talc. The method of measuring water solubility is described in more detail below.
Detersive surfactant: a preferred detersive surfactant is alkyl benzene sulphonate. Suitable detersive surfactants include anionic detersive surfactants, nonionic detersive surfactants, cationic detersive surfactants, zwitterionic detersive surfactants, and amphoteric detersive surfactants. Suitable detersive surfactants can be linear or branched, substituted or unsubstituted, and can be derived from petrochemical or biological materials.
Anionic detersive surfactant: suitable anionic detersive surfactants include sulphonate detersive surfactants and sulphate detersive surfactants.
Suitable sulphonate detersive surfactants include methyl sulphonate, α olefin sulphonate, alkyl benzene sulphonate, especially alkyl benzene sulphonate, preferably C10-13An alkylbenzene sulfonate. Suitable alkyl benzene sulfonates (LAS) are available, preferably obtained by sulfonating commercially available Linear Alkyl Benzenes (LAB); suitable LAB include lower 2-phenyl LAB, other suitable LAB include higher 2-phenyl LAB, such as under the trade name LABThose supplied by Sasol.
Suitable sulphate detersive surfactants include alkyl sulphates, preferably C8-18Alkyl sulfates, or predominantly C12An alkyl sulfate.
Preferred sulphate detersive surfactants are alkyl alkoxylated surfactantsSulfates, preferably alkyl ethoxylated sulfates, preferably C8-18Alkyl alkoxylated sulfates, preferably C8-18Alkyl ethoxylated sulfates, preferably alkyl alkoxylated sulfates having an average degree of alkoxylation of from 0.5 to 20, preferably from 0.5 to 10, preferably the alkyl alkoxylated sulfate is C8-18Alkyl ethoxylated sulfates having an average degree of ethoxylation of from 0.5 to 10, preferably from 0.5 to 5, more preferably from 0.5 to 3, and most preferably from 0.5 to 1.5.
Alkyl sulfates, alkyl alkoxylated sulfates and alkyl benzene sulfonates may be linear or branched, substituted or unsubstituted, and may be derived from petrochemical or biological materials.
Other suitable anionic detersive surfactants include alkyl ether carboxylates.
Suitable anionic detersive surfactants can be in the form of salts, and suitable counterions include sodium, calcium, magnesium, amino alcohols, and any combination thereof. The preferred counterion is sodium.
Nonionic detersive surfactant: suitable nonionic detersive surfactants are selected from: c8-C18Alkyl ethoxylates, such as from ShellA nonionic surfactant; c6-C12Alkylphenol alkoxylates, wherein preferably the alkoxylate units are ethyleneoxy units, propyleneoxy units, or mixtures thereof; c12-C18Alcohol and C6-C12Condensates of alkylphenols with ethylene oxide/propylene oxide block polymers, such as those available from BASFAlkyl polysaccharides, preferably alkyl polyglycosides; a methyl ester ethoxylate; polyhydroxy fatty acid amides; ether-terminated poly (alkoxylated) alcohol surfactants; and mixtures thereof.
Suitable nonionic detersive surfactants are alkyl polyglucosides and/or alkyl alkoxylated alcohols.
Suitable nonionic detersive surfactants include alkyl alkoxylated alcohols, preferably C8-18Alkyl alkoxylated alcohols, preferably C8-18The alkyl ethoxylated alcohol, preferably the alkyl alkoxylated alcohol has an average degree of alkoxylation of from 1 to 50, preferably from 1 to 30, or from 1 to 20, or from 1 to 10, preferably the alkyl alkoxylated alcohol is C8-18An alkyl ethoxylated alcohol having an average degree of ethoxylation of from 1 to 10, preferably from 1 to 7, more preferably from 1 to 5, and most preferably from 3 to 7. The alkyl alkoxylated alcohol may be linear or branched, and substituted or unsubstituted.
Suitable nonionic detersive surfactants include secondary alcohol-based detersive surfactants.
Cationic detersive surfactant: suitable cationic detersive surfactants include alkyl pyridinium compounds, alkyl quaternary ammonium compounds, alkyl quaternary phosphonium compounds, alkyl ternary sulfonium compounds, and mixtures thereof.
Preferred cationic detersive surfactants are quaternary ammonium compounds having the general formula:
(R)(R1)(R2)(R3)N+X-
wherein R is a linear or branched, substituted or unsubstituted C6-18Alkyl or alkenyl moieties, R1And R2Independently selected from methyl or ethyl moieties, R3Is a hydroxyl, hydroxymethyl or hydroxyethyl moiety, X is an anion that provides electrical neutrality, preferred anions include: halide ions, preferably chloride ions; sulfate radical; and a sulfonate group.
Zwitterionic detersive surfactant: suitable zwitterionic detersive surfactants include amine oxides and/or betaines.
Carboxylate polymers: suitable carboxylate polymers include polymers such as maleate/acrylate random copolymers or polyacrylate homopolymers. Suitable carboxylate polymers include: a polyacrylate homopolymer having a molecular weight of 4,000Da to 9,000 Da; having a molecular weight of 30,000Da to 100,000Da, or 50,000Da to 100,000Da,Or a maleate/acrylate random copolymer having a molecular weight of from 60,000Da to 80,000 Da.
Another suitable carboxylate polymer is a copolymer comprising: (i) from 50 to less than 98 wt% structural units derived from one or more monomers comprising a carboxyl group; (ii) from 1 wt% to less than 49 wt% structural units derived from one or more monomers comprising a sulfonate moiety; and (iii)1 to 49 wt% of structural units derived from one or more types of monomers selected from ether bond-containing monomers represented by formulas (I) and (II):
formula (I):
wherein in formula (I), R0Represents a hydrogen atom or CH3Group, R represents CH2Radical, CH2CH2A group or a single bond, X represents a number from 0 to 5, with the proviso that when R is a single bond, X represents a number from 1 to 5, and R1Is a hydrogen atom or C1To C20An organic group;
formula (II)
Wherein in formula (II), R0Represents a hydrogen atom or CH3Group, R represents CH2Radical, CH2CH2A group or a single bond, X represents a number from 0 to 5, and R1Is a hydrogen atom or C1To C20An organic group.
It may be preferred that the polymer has a weight average molecular weight of at least 30kDa, or at least 50kDa, or even at least 70 kDa.
Free-flowing solid particulate laundry detergent composition: typically, the spray-dried granules prepared by the process of the present invention may be combined with other granules to form a free-flowing solid particulate laundry detergent composition which is a fully formulated laundry detergent powder compositionA compound (I) is provided. Typically, the solid composition comprises a plurality of chemically distinct particles, such as spray-dried base detergent particles in combination with one or more agglomerated detergent particles and/or extruded detergent particles. The spray-dried particles may be used in combination with one or more, typically two or more, or five or more, or even ten or more particles selected from: surfactant granules including surfactant agglomerates, surfactant extrudates, surfactant needles, surfactant bars, surfactant flakes; phosphate particles; zeolite particles; polymer particles such as carboxylate polymer particles, cellulosic polymer particles, starch particles, polyester particles, polyamine particles, terephthalic acid polymer particles, polyethylene glycol particles; aesthetic particles such as colored bars, needles, lamellar particles, and ring particles; enzyme granules, such as protease granules, amylase granules, lipase granules, cellulase granules, mannanase granules, pectate lyase granules, xyloglucanase granules, bleaching enzyme granules and co-granules of any of these enzymes, preferably the enzyme granules comprise sodium sulphate; bleach particles, such as percarbonate particles, in particular coated percarbonate particles, such as percarbonate coated with carbonate, sulphate, silicate, borosilicate, or any combination thereof, perborate particles, bleach activator particles such as tetraacetylethylenediamine particles and/or alkyloxybenzenesulfonate particles, bleach catalyst particles such as transition metal catalyst particles, and/or isoquinolinium bleach catalyst particles, preformed peracid particles, in particular coated preformed peracid particles; filler particles such as sulfate and chloride particles; clay particles such as montmorillonite particles and clay and silicone particles; flocculant particles, such as polyethylene oxide particles; wax particles, such as waxy agglomerates; silicone particles, brightener particles; dye transfer inhibitor particles; dye fixative particles; perfume particles, such as perfume microcapsules and starch encapsulated perfume accord particles, and pro-perfume particles, such as schiff base reaction product particles; a hueing dye particle; chelant particles, such as chelantsAn agglomerate; and any combination thereof.
The composition may comprise: silicate particles, especially sodium silicate particles; and/or carbonate particles, in particular sodium bicarbonate particles. However, it may be preferred that the composition is free of silicate particles, in particular free of sodium silicate particles. It may also be preferred that the composition is free of carbonate particles, in particular free of sodium carbonate particles.
Preferably, the composition comprises from 1 to 10 wt% of dry added acidic particles, preferably from 2 to 8 wt% of dry added acidic particles. Suitable dry-added acids are organic acids, preferably carboxylic acids, preferably cirtric acids.
Detergent composition: suitable laundry detergent compositions comprise detergent ingredients selected from the group consisting of: detersive surfactants such as anionic detersive surfactants, nonionic detersive surfactants, cationic detersive surfactants, zwitterionic detersive surfactants, and amphoteric detersive surfactants; polymers such as carboxylate polymers, soil release polymers, anti-redeposition polymers, cellulosic polymers and care polymers; bleaching agents such as sources of hydrogen peroxide, bleach activators, bleach catalysts and preformed peracids; photobleaches such as, for example, sulfonated zinc phthalocyanine and/or sulfonated aluminum phthalocyanine; enzymes such as proteases, amylases, cellulases, lipases; a zeolite builder; a phosphate builder; co-builders, such as citric acid and citrates; sulfates, such as sodium sulfate; chloride salts, such as sodium chloride; a whitening agent; a chelating agent; a toner; a dye transfer inhibiting agent; a dye fixative agent; a fragrance; an organosilicon; fabric softeners, such as clay; flocculants such as polyethylene oxide; a suds suppressor; and any combination thereof.
The composition may comprise: silicates, especially sodium silicate; and/or carbonates, especially sodium bicarbonate and/or sodium carbonate. However, it may be preferred that the composition is free of silicate, especially free of sodium silicate. It may also be preferred that the composition is carbonate-free, in particular sodium carbonate and/or sodium bicarbonate-free.
The composition may have a pH profile such that, when diluted in deionized water at a temperature of 20 ℃ at a concentration of 1g/L, the composition has a pH in the range of 7.0 to 9.5, or 7.0 to 9.0, or 7.0 to 8.5, or even 7.5 to 8.5.
Suitable laundry detergent compositions may have low buffering capacity. Such laundry detergent compositions typically have a reserve alkalinity to pH 7.5 of less than 5.0g naoh/100g, preferably less than 3.0g naoh/100 g.
The composition is preferably substantially free of preformed peracid. The composition is preferably substantially free of phthalimido-peroxycaproic acid. Substantially free means not intentionally added.
Detersive surfactant: suitable detersive surfactants are described above.
Polymer and method of making same: suitable polymers include carboxylate polymers, soil release polymers, anti-redeposition polymers, cellulosic polymers, care polymers, and any combination thereof.
Carboxylate polymers: suitable carboxylate polymers are described above.
Soil release polymers: the composition may comprise a soil release polymer. Suitable soil release polymers have a structure as defined by one of the following structures (I), (II) or (III):
(I)-[(OCHR1-CHR2)a-O-OC-Ar-CO-]d
(II)-[(OCHR3-CHR4)b-O-OC-sAr-CO-]e
(III)-[(OCHR5-CHR6)c-OR7]f
wherein:
a. b and c are 1 to 200;
d. e and f are 1 to 50;
ar is 1, 4-substituted phenylene;
sAr is SO at position 531, 3-substituted phenylene substituted with Me;
me is Li, K, Mg/2, Ca/2, Al/3, ammonium, monoalkylammonium, dialkylammonium,trialkylammonium or tetraalkylammonium in which the alkyl radical is C1-C18Alkyl or C2-C10Hydroxyalkyl or mixtures thereof;
R1、R2、R3、R4、R5and R6Independently selected from H or C1-C18N-alkyl or C1-C18An isoalkyl group; and
R7is straight-chain or branched C1-C18Alkyl, or straight or branched C2-C30Alkenyl, or cycloalkyl having 5 to 9 carbon atoms, or C8-C30Aryl, or C6-C30An arylalkyl group.
Suitable soil release polymers are prepared from Clariant andseries of polymers sold, e.g.
anti-redeposition polymers: suitable anti-redeposition polymers include polyethylene glycol polymers and/or polyethyleneimine polymers.
Suitable polyethylene glycol polymers include random graft copolymers comprising: (i) a hydrophilic backbone comprising polyethylene glycol; and (ii) one or more hydrophobic side chains,the one or more hydrophobic side chains are selected from: c4-C25Alkyl radical, polypropylene, polybutylene, saturated C1-C6Vinyl esters of monocarboxylic acids, C of acrylic or methacrylic acid1-C6Alkyl esters, and mixtures thereof. Suitable polyethylene glycol polymers have a polyethylene glycol backbone with randomly grafted polyvinyl acetate side chains. The average molecular weight of the polyethylene glycol backbone may be in the range of 2,000Da to 20,000Da, or 4,000Da to 8,000 Da. The molecular weight ratio of the polyethylene glycol backbone to the polyvinyl acetate side chains can range from 1:1 to 1:5, or from 1:1.2 to 1: 2. The average number of grafting sites per 50 ethylene oxide units may be less than 1, or less than 0.8, the average number of grafting sites per ethylene oxide unit may be in the range of 0.5 to 0.9, or the average number of grafting sites per ethylene oxide unit may be in the range of 0.1 to 0.5, or 0.2 to 0.4. A suitable polyethylene glycol polymer is Sokalan HP 22. Suitable polyethylene glycol polymers are described in WO 08/007320.
Cellulose polymers: suitable cellulosic polymers are selected from alkyl celluloses, alkyl alkoxyalkyl celluloses, carboxyalkyl celluloses, alkyl carboxyalkyl celluloses, sulfoalkyl celluloses, more preferably from carboxymethyl cellulose, methyl hydroxyethyl cellulose, methyl carboxymethyl cellulose and mixtures thereof.
Suitable carboxymethyl celluloses have a degree of carboxymethyl substitution of 0.5 to 0.9 and a molecular weight of 100,000Da to 300,000 Da.
Suitable carboxymethyl celluloses have a degree of substitution greater than 0.65 and a degree of blockiness greater than 0.45, for example as described in WO 09/154933.
Care polymers: suitable care polymers include cationically modified or hydrophobically modified cellulosic polymers. Such modified cellulosic polymers can provide anti-abrasion benefits and dye lock benefits to fabrics during the wash cycle. Suitable cellulosic polymers include cationically modified hydroxyethyl cellulose.
Other suitable care polymers includeDye-locking polymers, such as condensation oligomers produced by condensation of imidazole and epichlorohydrin, preferably in a 1:4:1 ratio. Suitable commercially available dye-locking polymers areFDI(Cognis)。
Other suitable care polymers include amino-silicones, which can provide fabric feel benefits and fabric shape retention benefits.
Bleaching agent: suitable bleaching agents include sources of hydrogen peroxide, bleach activators, bleach catalysts, preformed peracids, and any combination thereof. Particularly suitable bleaching agents include a hydrogen peroxide source in combination with a bleach activator and/or bleach catalyst.
Hydrogen peroxide source: suitable sources of hydrogen peroxide include sodium perborate and/or sodium percarbonate.
Bleach activators: suitable bleach activators include tetraacetylethylenediamine and/or alkylphenol sulfonates.
Bleaching catalyst: the composition may comprise a bleach catalyst. Suitable bleach catalysts include the peroxyimine cation bleach catalysts, transition metal bleach catalysts, especially manganese and iron bleach catalysts. Suitable bleach catalysts have a structure corresponding to the general formula:
wherein R is13Selected from the group consisting of 2-ethylhexyl, 2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, isononyl, isodecyl, isotridecyl and isotentadecyl.
Preformed peracids: suitable preformed peracids include phthalimido-peroxycaproic acid.
Enzyme: suitable enzymes include lipases, proteases, cellulases, amylases, and any combination thereof.
Protease:suitable proteases include metalloproteases and serine proteases. Examples of suitable neutral or alkaline proteases include: subtilisin (EC 3.4.21.62); trypsin-type or chymotrypsin-type proteases; and a metalloprotease. Suitable proteases include chemically modified or genetically modified mutants of the aforementioned suitable proteases.
Suitable commercially available proteases include those under the trade name
Suitable proteases are described in WO11/140316 and WO 11/072117.
AmylaseSuitable amylases are derived from AA560 α amylase endogenously derived from Bacillus DSM 12649, preferably with the following mutations R118K, D183, G184, N195F, R320K and/or R458KCommercially available amylases of (a) include Plus、Natalase、Ultra、SZ、(both from Novozymes) and
Suitable amylases are described in WO 06/002643.
Cellulase enzymes: suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are also suitable. Suitable cellulases include cellulases from the genera Bacillus, Pseudomonas (Pseudomonas), Humicola (Humicola), Fusarium (Fusarium), Rhizopus (Thielavia), Acremonium (Acremonium), for example from Humicola insolens, Myceliophthora thermophila and Fusarium oxysporum (Fusar)An ium oxysporum) produced fungal cellulase.
Commercially available cellulases include
Lipase enzyme: suitable lipases include those of bacterial, fungal or synthetic origin, as well as variants thereof. Chemically modified or protein engineered mutants are also suitable. Examples of suitable lipases include lipases from humicola (the synonym Thermomyces), for example from humicola lanuginosa (h.lanuginosa) (Thermomyces lanuginosus) sp.
The lipase may be a "first cycle lipase", for example, such as those described in WO06/090335 and WO 13/116261. In one aspect, the lipase is a first wash lipase, preferably from thermomyces lanuginosus comprising a T231R and/or N233R mutationA variant of the wild-type lipase of (1). Preferred lipases include those known under the trade nameAndthose sold by Novozymes (Bagsvaerd, Denmark).
Other suitable lipases include: lipr 1139, e.g. as described in WO 2013/171241; and TfuLip2, for example as described in WO2011/084412 and WO 2013/033318.
Other enzymes: other suitable enzymes are bleaching enzymes such as peroxidases/oxidases, including those of plant, bacterial or fungal origin, and variants thereof. Commercially available peroxidases include(Novozymes A/S). Other suitable enzymes include choline oxidase and perhydrolase, such as for Gentle Power BleachTMOf (a).
Other suitable enzymes include those known under the trade name
Other suitable enzymes include nucleases, such as deoxyribonuclease.
Zeolite builders: the composition may comprise a zeolite builder. The composition canComprises from 0 wt% to 5 wt% zeolite builder, or 3 wt% zeolite builder. The composition may even be substantially free of zeolite builder; substantially free means "not intentionally added". Typical zeolite builders include zeolite a, zeolite P and zeolite MAP.
Phosphate builders: the composition may comprise a phosphate builder. The composition may comprise from 0 wt% to 5 wt% phosphate builder, or to 3 wt% phosphate builder. The composition may even be substantially free of phosphate builder; substantially free means "not intentionally added". A typical phosphate builder is sodium tripolyphosphate.
Carbonate salt: the composition may comprise a carbonate salt. The composition may comprise 0 wt% to 5 wt% carbonate. The composition may even be substantially free of carbonate; substantially free means "not intentionally added". Suitable carbonates include sodium carbonate and sodium bicarbonate.
Silicates of acid or alkali: the composition may comprise a silicate. The composition may comprise 0 wt% to 5 wt% silicate salt. The composition may even be substantially free of silicate; substantially free means "not intentionally added". The preferred silicate is sodium silicate, particularly preferred is Na having a value of 1.0 to 2.8, preferably 1.6 to 2.02O:SiO2Sodium silicate in a ratio.
Sulfates of sulfuric acid: a suitable sulfate salt is sodium sulfate.
Whitening agent: suitable optical brighteners include: distyrylbiphenyl compounds, e.g.CBS-X, diaminostilbene disulfonic acid compounds, e.g.
Preferred whitening agents are: sodium 2- (4-styryl-3-sulfophenyl) -2H-naphthol [1,2-d ] triazole, disodium 4,4 ' -bis { [ (4-anilino-6- (N-methyl-N-2-hydroxyethyl) amino 1,3, 5-triazin-2-yl) ] amino } stilbene-2-2 ' disulfonate, disodium 4,4 ' -bis { [ (4-anilino-6-morpholino-1, 3, 5-triazin-2-yl) ] amino } stilbene-2-2 ' disulfonate, and disodium 4,4 ' -bis (2-sulfostyryl) biphenyl. Suitable optical brighteners are c.i. Fluorescent whitening agent 260, which may be used in its beta or alpha crystalline form or a mixture of these crystalline forms.
Chelating agents: the composition may further comprise a chelating agent selected from: diethylene triamine pentaacetate, diethylene triamine penta (methyl phosphonic acid), ethylene diamine-N' -disuccinic acid, ethylene diamine tetraacetate, ethylene diamine tetra (methylene phosphonic acid), and hydroxyethane di (methylene phosphonic acid). Preferred chelating agents are ethylenediamine-N' -disuccinic acid (EDDS) and/or hydroxyethane diphosphonic acid (HEDP). The composition preferably comprises ethylenediamine-N' -disuccinic acid or salts thereof. Preferably ethylenediamine-N 'N' -disuccinic acid is in the form of the S, S enantiomer. Preferably, the composition comprises 4, 5-dihydroxy-m-benzenedisulfonic acid disodium salt. Preferred chelating agents may also act as calcium carbonate crystal growth inhibitors, such as: 1-hydroxyethane diphosphoric acid (HEDP) and salts thereof; n, N-dicarboxymethyl-2-aminopentane-1, 5-dioic acid or its salt; 2-phosphonobutane-1, 2, 4-tricarboxylic acid and salts thereof; and combinations thereof. A suitable chelating agent is MGDA.
Toner and image forming apparatus: suitable hueing agents include small molecule dyes, typically falling within the following color index (c.i.) classification: acid dyes, direct dyes, basic dyes, reactive dyes (including hydrolyzed forms thereof), or solvent dyes or disperse dyes, such as dyes classified as blue, violet, red, green, or black, and providing a desired hue, either individually or in combination. Preferred such hueing agents include acid violet 50Direct violet 9, 66 and 99, solvent violet 13, and any combination thereof.
Many toners suitable for use in the present invention are known and described in the art, such as the toners described in WO 2014/089386.
Suitable hueing agents include phthalocyanine and azo dye conjugates, such as described in WO 2009/069077.
Suitable toners may be alkoxylated. Such alkoxylated compounds may be prepared by organic synthesis, which may result in a mixture of molecules having different degrees of alkoxylation. Such mixtures may be used directly to provide a toner, or may be subjected to a purification step to increase the proportion of target molecules. Suitable hueing agents include alkoxylated disazo dyes, such as described in WO2012/054835, and/or alkoxylated thiophene azo dyes, such as described in WO2008/087497 and WO 2012/166768.
The hueing agent may be incorporated into the detergent composition as part of the reaction mixture as a result of the organic synthesis of the dye molecule by one or more optional purification steps. Such reaction mixtures generally comprise the dye molecules themselves and may, in addition, comprise unreacted starting materials and/or by-products of organic synthesis pathways. Suitable hueing agents may be incorporated into the hueing dye particles, such as described in WO 2009/069077.
Dye transfer inhibitors: suitable dye transfer inhibiting agents include polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone, polyvinyloxazolidone, polyvinylimidazole, and mixtures thereof. Preferred are poly (vinylpyrrolidone), poly (vinylpyridine betaine), poly (vinylpyridine N-oxide), poly (vinylpyrrolidone-vinylimidazole), and mixtures thereof. Suitable commercially available dye transfer inhibitors include PVP-K15 and K30(Ashland),
Spice: suitable perfumes include perfume materials selected from the group consisting of: (a) a perfume material having a ClogP of less than 3.0 and a boiling point of less than 250 ℃ (quadrant 1 perfume material); (b) perfume materials having a ClogP of less than 3.0 and a boiling point of 250 ℃ or greater (quadrant 2 perfume materials); (c) perfume materials having a ClogP of 3.0 or greater and a boiling point of less than 250 ℃ (quadrant 3 perfume materials); and (d) a perfume material having a ClogP of 3.0 or greater and a boiling point of 250 ℃ or greater (quadrant 4 perfume material); and (e) mixtures thereof.
It may be preferred for the perfume to be in the form of a perfume delivery technology. Such delivery techniques are also stable and enhance deposition and release of perfume materials from laundered fabrics. Such perfume delivery technologies can also be used to further increase the longevity of perfume release from laundered fabrics. Suitable perfume delivery technologies include: perfume microcapsules, pro-perfumes, polymer assisted delivery, molecular assisted delivery, fiber assisted delivery, amine assisted delivery, cyclodextrins, starch encapsulated accords, zeolites and other inorganic carriers, and any mixtures thereof. Suitable perfume microcapsules are described in WO 2009/101593.
Siloxanes: suitable silicones include polydimethylsiloxane and amino-siloxanes. Suitable siloxanes are described in WO 05075616.
Method for measuring bulk density: one suitable method of measuring bulk density is adapted from ISO method No. 34241975E. The method includes a funnel with a lid on the bottom to temporarily hold the powder to be measured and a 500mL cup using the specifications described in the ISO method. The bulk density was measured as follows: the powder sample was placed on the funnel while the bottom closure cap was closed. A500 mL cylindrical cup was weighed and peeled on a scale having at least 2 decimal places. The cup is then placed on the bottom of the funnel. By opening the closure, the powder is released freely from the funnel, thereby allowing the powder to flow freely and fill the cup.The powder was carefully leveled with a saw-tooth motion using a straight edge to avoid additional vibration. Once the powder has been leveled, the cups that have previously been peeled off on the balance are weighed. The weight of the powder in a 500ml container was multiplied by 2 to obtain the bulk density (g/l)
Method for measuring weight average particle size: the weight average particles can be measured using a dynamic image analyzer (e.g., the Camsizer by Retzsch). Powder samples were taken online by an autosampler. Approximately 15g of blown powder was sampled and measured using a vibrating aluminum feeder with the speed start level set at 40% and a nominal area of 3%. The particles fall between the planar light sources with two CCD cameras. The shadow cast by the particles was analyzed and the median particle size was calculated based on the calculated volume (assuming spherical particles) using the software provided by the manufacturer (D50). The analysis took approximately 1200 images in 1 minute.
Method for measuring water solubility: a suitable method uses a2 gram (on a solids basis, excluding water content) sample (such as silicate) in 100 grams of total solution using deionized water. The samples were maintained at 20 ℃ using a water bath as required. The mixture was placed in a 500mL beaker having a diameter of 80mm, a stir bar length of 50mm, and set at 500 rpm. The mixture is mixed for 30 minutes to allow the sample to dissolve and/or disperse. Once the mixture has been thoroughly mixed, it is then passed through a stainless steel filter having a pore size of 25 microns (25 μm). Filtration used a three-piece glass buchner funnel (9cm diameter), a 1L flask, and a vacuum pump with a water trap and a 9cm diameter stainless steel filter. A pre-weighed stainless steel dry filter was placed on a buchner funnel. The previously mixed mixture was poured onto the filter while the vacuum pump was switched on. Once all the liquid has completely drained the filter, the vacuum pump is stopped. The stainless steel filter with the wet residue was then placed inside an oven at 100 ℃ for 24 hours to dry. The filter was then reweighed. The difference between this weight and the initial weight before filtration was regarded as the weight of insoluble matter remaining on the filter. The percentage of insolubles was calculated. For the purposes of the present invention, it is typical to have less than 0.50 in the above-described process% or more of any silicates that are insoluble are considered water insoluble silicates.
Sodium silicate 1.6R left 0.135% insoluble. Magnesium silicate left 69.06% insoluble material.
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