JPH0471960B2 - - Google Patents

Description

[Detailed description of the invention]

FIELD OF THE INVENTION This invention relates to detergent compositions, and more particularly to detergent compositions for washing and softening textiles. In general, detergent compositions, in addition to detergent actives for removing soil from textiles, also contain detergent builder substances, the role of which is primarily to prevent calcium ions in hard water from reducing the efficiency of detergent actives. There is a particular thing. For many years, phosphates, such as sodium tripolyphosphate, have been used as detergent builders. For a number of reasons, it has become desirable to provide detergent compositions that contain no or very little phosphorus. A number of alternative phosphorus-free builders have been proposed, in particular mixtures of alkali metal carbonates, such as sodium carbonate, and calcium carbonate seed crystal materials, such as calcite [UK Patent No. 1437950: Unilever Corporation]. Compositions containing such builders are also relevant to the present invention. When sodium carbonate/calcite builder mixtures are used in place of sodium tripolyphosphate, a number of differences appear, especially the tendency to deteriorate the feel of the fabric. Harshening
This is a phenomenon that occurs with many detergent compositions and causes the fabric to feel worse after washing. This occurs particularly in the case of fabrics made of natural fibers, such as cotton, and is caused in part by the removal of natural lubricating substances from the fibers of the fabric. A number of materials have been proposed in the art as fabric softeners that can reduce the extent of this poor feel during laundering. Materials of this type are smectite clays with a high exchange capacity, such as those disclosed in GB 1400898 (Procter & Gamble). however,
It has been found that this type of clay is most effective when used in the presence of a peptizer, such as sodium tripolyphosphate. However, these clays are less effective in the absence of tripolyphosphate ions. Therefore, the art does not recommend clays as effective fabric softening or anti-feel agents for use with detergent compositions in which alkali metal carbonates are used in place of tripolyphosphates. It has now been found that the fabric feel degrading effects of compositions containing sodium carbonate/calcite builder mixtures can be substantially eliminated by the presence of fabric softening clay materials. According to the invention, therefore: () 2-40% by weight of at least one non-soap detergent active; () 5-40% by weight of a builder substance comprising a water-soluble carbonate; () 10-40% by weight of at least one non-soap detergent active; Consisting of 60% by weight water-insoluble calcium carbonate seed crystals and up to 35% by weight textile softening clay material, with a weight ratio of seed crystals to clay material of 1.8:1
There is provided a detergent composition for washing and softening textiles, characterized in that the detergent composition is less than The compositions according to the invention necessarily contain at least one non-soap detergent active, preferably in an amount of 5 to 40% by weight. These substances are preferably selected from non-soap anionic and non-ionic detergent actives and mixtures thereof. Other detergent actives such as soaps may also be used, but are generally mixed with non-soap anionic and/or non-ionic materials. Non-soap (synthetic) anionic detergent active compounds are
Generally, water-soluble alkali metal salts of organic sulfate and sulfonic acid compounds having alkyl groups having from about 8 to about 22 carbon atoms, where the term alkyl includes the alkyl portion of higher acyl groups. used for. Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher ( _C8 - _C18 ) alcohols produced, for example, from tallow or coconut oil; alkyl ( _C9) ~ _C20 ) Sodium and potassium benzenesulfonates, especially straight-chain secondary alkyl ( _C10 - _C15 ) sodium benzenesulfonates; sodium alkyl glyceryl ether sulfates, especially higher alcohols obtained from tallow or coconut oil and petroleum. ethers of synthetic alcohols; coco aliphatic monoglycerides sulfate and sodium sulfonate; sodium and potassium salts of sulfate esters of higher ( _C8 - _C18 ) aliphatic alcohol-alkylene oxide (especially ethylene oxide) reaction products; isethion; Reaction products of fatty acids, such as coco fatty acids, esterified with acids and neutralized with sodium hydroxide; sodium and potassium salts of fatty acid amides of methyltaurine; e.g. α-olefins (C ₈ -C ₂₀ ) alkane monosulfonates, such as those obtained by reacting paraffin with sodium bisulfite and by reacting paraffin with SO ₂ and Cl ₂ and subsequently hydrolyzing it with base to form random sulfonates; and olefin sulfonates. (This term is used to designate substances produced by reacting olefins, especially _C10 - _C20 α-olefins, with _SO3 and then neutralizing and hydrolyzing the reaction product.) ). Suitable anionic detergent compounds are ( _C11 - _C15 ) sodium alkylbenzene sulfonates and ( _C16 - _C18 ) sodium alkyl sulfates. Suitable nonionic detergent compounds include, in particular, compounds having hydrophobic groups and reactive hydrogen atoms (for example aliphatic alcohols, acids, amides or alkylphenols) and alkylene oxides (in particular ethylene oxide alone or in mixtures with propylene oxide). Includes reaction products with. Particular nonionic detergent compounds are alkyl (C ₆ -C ₂₂ ) phenol-ethylene oxide condensates, generally having up to 25 EO, i.e., up to 25 units of ethylene oxide per molecule, aliphatic (C ₈ -C ₁₈ ) Condensation products of primary or secondary straight-chain or branched-chain alcohols with ethylene oxide, generally up to 40 EO; It is a substance that can be Other so-called non-ionic detergent compounds include long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulfoxides. From the point of view of preventing deterioration of feel, it has been found to be particularly advantageous if the detergent active system is a mixture of soap and non-soap anionic detergent actives and, if necessary, also contains non-ionic detergent actives. . Particularly preferred detergent active systems contain 2-17% non-soap anionic detergent actives, up to 8% non-ionic detergent actives, and up to 8% soap;
It has a ratio of non-ionic active ingredient to soap of from 1 to 1:3, particularly preferably from 2:1 to 1:2. As used herein, the term "soap" refers to not only the usual alkali metal and alkaline earth metal salts of fatty acids, but also fatty acids to organic nitrogen-containing substances,
Also included are organic salts, such as those that can be produced in complexes with amines and their derivatives. In general, soaps consist of salts of higher fatty acids or mixtures thereof having 8 to 24 carbon atoms, preferably 10 to 20 carbon atoms in the molecule. Examples of suitable soaps are sodium stearate; sodium palmitate; sodium salts of tallow, coco-coconut oil and coconut oil fatty acids; and stearic acid and/or palmitic acid and/or tallow and/or coco-coconut oil and/or coconut oil. Combinations of fatty acids with water-soluble alkanolamines such as ethanolamine, di- or tri-ethanolamine and 2,2-dimethylethanolamine, and N-containing cyclic compounds such as morpholine, 2'-pyrrolidone and its methyl derivatives. Including complexes between. Mixtures of soaps can also be used. Particularly preferred are the sodium and potassium salts of mixed fatty acids obtained from coconut oil and tallow, ie sodium and potassium tallow and coconut oil soaps. An essential component of this composition is a water-soluble carbonate material as a builder. This is preferably sodium or potassium carbonate or a mixture thereof. However, in the present invention it has been found to be particularly advantageous if the water-soluble carbonate material contains some degree of bicarbonate. That is, the carbonate can be fully neutralized, but preferably partially neutralized, for example sesquicarbonate can be used to replace part of the regular carbonate. A preferred weight ratio of carbonate to bicarbonate is from 10:1 to 1:2, particularly preferably from 6:1 to 1:1. The amount of water-soluble carbonate material in the detergent composition may vary over a wide range, but it should be at least 5% by weight, such as from 10 to 40%, preferably from 10 to 35%. Although the amount of water-soluble carbonate material is determined on an anhydrous basis, these salts can also be hydrated before or during incorporation into the detergent composition. It should also be noted that it is also desirable to limit the carbonate content to a low level within the above range to reduce the risk of internal damage in case of accidental ingestion, such as by children. Within limits of up to 40% of the builder substances in the compositions of the invention, other builder substances may be present, but substances that act as seed crystal poisons are best avoided. Other art-recognized examples of builder materials of this type include fatty acids, selected water-soluble soaps, alkyl malonates, alkenyl or alkyl succinates, sodium sulfonates of fatty acids, alkali metal oligophosphates, polyesters, Included are acetates, carboxylates, polycarboxylates, succinates and zeolites or their amorphous equivalents. The composition necessarily also contains water-insoluble particulate carbonate material. This material must be capable of acting as a seed crystal for the precipitate resulting from the reaction between the water's calcium hardness ions and the water-soluble carbonates. That is, this water-insoluble particulate material is a seed crystal for calcium carbonate, such as calcium carbonate itself. The water-insoluble particulate carbonate material should be finely divided and have a surface area of at least 10 m ² /g, preferably at least 15 m ² /g. 30−100
Particularly preferred are those with a surface area of m ² /g.
Insoluble carbonate materials with surface areas greater than 100 m ² /g can also be used if these materials are economically available. The surface area is the standard Blauer, Emmett and
Measured by nitrogen adsorption using Teller (BET) method. Suitable equipment for carrying out this method is the Carlo Erba Thorpey, which is operated according to the manufacturer's guidelines.
Sorpty) 1750 type device. It is particularly preferred to create a high surface area material in the absence of toxicants to retain its seeding activity. Insoluble carbonate materials generally have an average particle size of less than 10 μm as determined by sieve analysis, but can also be granulated for ease of handling. If the insoluble carbonate material is calcium carbonate, any crystalline form or mixture thereof may be used, but calcite is preferred. This is because argonite and vaterite are not readily available commercially and calcite is slightly less soluble than argonite or vaterite, especially at normal washing temperatures. When using argonite or vaterite,
This is generally as a mixture with calcite. In the general description below, "calcite"
The term refers to either calcite itself or any other suitable water-insoluble calcium carbonate seed material. The selected level of calcite for the total composition is
Depends on the specific surface area as mentioned above. The amount of calcite used in the composition should be between 10 and 60%, more preferably between 15 and 30%. A weight ratio of water-soluble carbonate material to calcite of less than about 4:1 is preferred. Another essential component of the composition according to the invention is a fabric softening clay material. The clay material should be a phyllosilicate clay with a 2:1 layer structure, where the non-silicate layer can be either dioctahedrally or trioctahedrally coordinated and is composed of saponite, hetocrite, montmorillonite or Includes types of beidellite. For example, talc,
Other 2:1 clay materials such as vermiculite, mica and chlorite have been found to be unsuitable for fabric softening, as well as the 1:1 clay materials of the kaolin group.
Unaltered minerals such as layered clays are also unsuitable. Other aluminosilicate materials that do not have a layered structure, such as zeolites, are also unsuitable as textile softening clay materials. Particularly suitable clay materials are the smectite clays described in detail in U.S. Pat. No. 3,959,155 (Montgomerer et al., Procter & Gamble Company), especially the smectite clays described in detail in, for example, U.S. Pat. No. 3,936,537 (Baskerville Company). It is a smectite clay as described. Other disclosures of clay materials suitable for textile softening purposes are found in European Patent No. 26528-A (Procter & Gamble Limited). Particularly suitable clay fabric softening materials include bentonite-based materials, where bentonite is primarily a montmorillonite type of clay and contains various impurities, the amount and nature of which depends on the source of the clay material. The amount of fabric softening clay material in the compositions of the invention should be sufficient to impart softening properties to the fabric. Amounts of up to 35% by weight, preferably 8 to 15% by weight, based on the composition, are suitable; these proportions refer to the amount of clay material itself. More clay raw material than this amount may be required if the clay material is obtained from a particularly impure raw material. The weight ratio of seed to clay should be less than 1.8:1. It has been found that when using higher ratios, such as 3.0:1, the fabric softness properties obtained from the clay are insufficient. If desired, the detergent composition can also contain any conventional ingredients in amounts such as those commonly used in textile laundry detergent compositions. One such optional component is an alkali metal silicate, especially sodium neutral, alkaline, meta- or ortho-silicate. Low levels of silicates, such as 5-10% by weight, are generally advantageous in reducing corrosion of metal parts in textile washing machines and provide additional processing advantages. Higher amounts such as 10-20% by weight, practically up to 30
% of silicates, an even more pronounced improvement in detergent properties is observed, which makes it possible to reduce the content of water-soluble carbonate substances to some extent. This effect appears to be particularly advantageous when the wash liquor is used with water having a significant amount of magnesium hardness. Additionally, the amount of silicate is generally about 90% per aqueous solution of the composition at the recommended concentration.
The above can be used to some extent to adjust the equilibrium PH of the washing liquid, which is preferably 10-11. Although sodium silicate is generally supplied as a concentrated aqueous solution, these amounts are calculated based on the anhydride amount. Examples of other optional ingredients are foam promoters such as alkanolamines (in particular monoethanolamide derived from coconut kernel fatty acids and coconut fatty acids), foam suppressants such as sodium perborate and sodium percarbonate. oxygen-releasing bleaches such as peracid bleach precursors, chlorine-releasing bleaches such as trichloroisocyanuric acid, other fabric softeners, inorganic salts such as sodium sulfate, and fluorescent agents, which are generally present in small amounts. , fragrances, enzymes such as proteases and amylases, fungicides and colorants. The detergent composition can be manufactured by any technique commonly used in the manufacture of textile laundry detergent compositions, including slurry making methods and spray drying methods. For example, the composition may consist of spray-dried beads containing at least part, e.g., all, of a detergent active system and a water-soluble carbonate, with calcite or other seed crystals added as separate particles that may be pregranulated. can do. The clay material can be included as a slurry to the spray-dried beads, or it can be added to the composition separately as a powder or pre-granulated material. Alternatively, if the composition contains sodium silicate, this may be prepared by granulating a carbonate/silicate powder with a seed crystal material, ideally in the presence of a liquid binder, such as a sucrose solution. This is described in detail in South African Patent No. 87/8350 (Unilever PLC). Hereinafter, the invention will be explained in more detail by way of non-limiting examples. In these examples, the following compositions were made by spray drying some ingredients to create a base powder and then adding the other ingredients thereto.

【table】

Table: Example 1 Composition A was tested in the following manner. Consisting of a mixture of pre-washed and textured terry cotton cloth
Wash 2.5Kg of textile laundry in an automatic washing machine at 40℃ or
Washed at 95°C for 30 minutes. The water hardness was 24°FH and the amount of product added was 140g in 20ml of washing liquid. A similar wash liquor was also made containing the same amount of Composition A along with 17 grams of clay, thus corresponding to Composition B containing about 12% clay. After each wash, the fabric was line dried and washed again.
After washing five times in this manner, the softness of the fabric was determined by a panel of experienced evaluators. The results were expressed as preferred numbers. The higher the scale, the greater the flexibility of the fabric. The results were as follows:

[Table] These results show that after 5 washes at both wash temperatures, Product B containing post-loaded clay was rated as more flexible than an otherwise identical product containing no clay. It shows that Example 2 Compositions A and D were tested as in Example 1, except that the laundry was a naturally soiled item, the wash temperature was 60° C., and 70 g of product was used for pre-washing each wash. After that, 140g of product was used for main washing. Water hardness was 40°FH and softness measurements were made after two and six washes. The results were as follows:

TABLE These results demonstrate the advantages of the present invention in incorporating viscosity into the spray dried base powder. When Composition D was modified by post-dosing with clay and calcite and the modified composition was tested, the flexibility performance was found to be very similar to Composition D. Example 3 Compositions G-J were tested as in Example 1, except that the wash temperature was 60 DEG C. and the product dosage was 7.7 g/kg. Instead of an automatic washing machine, a laboratory-scale apparatus equipped with an impeller agitator was used, and the textile laundry consisted of prewashed terry cotton fabric. Softness was measured after one wash.
The initial pH of the washing liquid was measured in each case. The results were as follows:

Table: These results demonstrate the benefit of sequentially replacing a portion of the carbonate with bicarbonate, thereby reducing the PH of the wash liquor. When compositions G and J were similarly tested at either 40°C or 60°C and the textile laundry used two different standard cotton detergent test fabrics, the observed % detergent properties were as follows: Ta:

[Table] In the table, Δ95 is the confidence limit for a significant difference with a 95% probability. It will be seen that although Composition J exhibits a lower PH and is preferred in terms of softening, there is no significant difference in the detergent properties observed. Example 4 Compositions KP were tested as in Example 3 and the softness was measured after one wash. The results were as follows:

Table: These results not only demonstrate the benefits of adding bicarbonate to the composition, but also show the benefits of including higher levels of soap and non-ionic active ingredients in the absence of bicarbonate. It also shows that.

Claims (1)

[Scope of Claims] 1 () 2-40% by weight of a detergent active system; () 5-40% by weight of a builder substance containing a water-soluble carbonate; () 10-60% by weight of a water-insoluble carbonic acid. A detergent composition for washing and softening textiles comprising calcium seed crystals, further comprising up to 35% by weight of a textile softening clay material, wherein the weight ratio of seed crystals to clay material is 1.8:
A detergent composition characterized in that the detergent composition is less than 1. 2. A composition according to claim 1, characterized in that the water-soluble carbonate builder substance comprises a mixture of alkali metal carbonates and alkali metal bicarbonates. 3. Composition according to claim 1, characterized in that the detergent active system comprises a mixture of soap and non-soap anionic detergent actives. 4. Composition according to claim 3, characterized in that the detergent active system further comprises a non-ionic detergent active. 5 characterized in that at least part of the detergent active system and the water-soluble carbonate builder substance is present in the form of spray-dried granules, and the remaining components, including at least part of the seed crystals, are present in the form of separate particles. The composition according to claim 1.