KR100505814B1 - Multipurpose liquid detergent composition - Google Patents

Abstract

The present invention relates to a multi-purpose liquid detergent composition which comprises at least one anionic surfactant, comprises a nonionic or amphoteric surfactant or a mixture thereof and comprises an excess salt. The detergent composition of the present invention shows improved emulsification and detergency in the neutral pH range against greasy or oily soil. Thus, the detergent composition of the present invention is suitable for kitchen detergents, grease or oily floor cleaners and floor and bathroom detergent applications requiring removal of grease or oily contamination.

Description

Multipurpose liquid detergent composition

The present invention relates to a multi-purpose liquid detergent composition which comprises at least one anionic surfactant, comprises a nonionic or amphoteric surfactant or a mixture thereof and comprises an excess salt. The detergent composition of the present invention shows improved emulsification and detergency in the neutral pH range against greasy or oily soil. Thus, the detergent composition of the present invention is suitable for kitchen detergents, grease or oily floor cleaners and floor and bathroom detergent applications requiring removal of grease or oily contamination.

Among various applications of surfactants, their use as detergents is the oldest and most widely used. However, since surfactants have excellent cleaning power according to their structural characteristics, there are practically no surfactants having excellent cleaning power under various cleaning conditions. As such, most detergents use a combination of two or more surfactants (US Pat. No. 5,298, 195). For example, anionic surfactants and nonionic or amphoteric surfactants are used together in the kitchen or floor and bathroom detergent applications where removal of grease or oily contamination is a problem (see US Pat. No. 5,589,447). In addition, builders (see European Patent No. 9,193), abrasives (see US Patent No. 4,797,231), divalent ion metal compounds (see US Patent No. 5,376,310), and the like are used as detergent compositions to improve cleaning power. Doing.

However, due to the various cleaning conditions, current formulations have different compositional characteristics depending on the use to show better cleaning power under limited cleaning conditions rather than being universally used for different cleaning conditions. For example, in the case of kitchen detergents for a long time in contact with the skin, it is common to maintain a neutral pH to avoid irritation to the skin. In addition, in the case of floor and bathroom detergents used for various rough surfaces, builders are added to improve emulsifying power and cleansing power to remove a large amount of contamination, and are irritating to the skin but have an alkali pH value. This is because generally, the cleaning power is better in alkaline conditions than in acidic or neutral conditions at room temperature (Tokyl Patent No. 27 09 690).

However, in practice, consumers often use dishwashing detergent to clean a lot of contamination on the surface, or conversely, floor and bathroom detergents are used to wash dishes. However, the compositional differences mentioned above do not give satisfactory results.

Therefore, it has overcome the limitations of the existing limited use by showing builders against grease or oily contamination with neutral pH that is not irritating to the skin and showing improved emulsification and cleaning power of the detergent composition level with alkali pH. There is a need for a prescription that can be used extensively.

Therefore, the present inventors, while studying to solve this problem, the emulsifying power and detergency is remarkable when an excessive amount of salt is present in the surfactant formulation that necessarily includes an anionic surfactant and includes a nonionic or amphoteric surfactant or a mixture thereof. It was found to be improved.

This improvement in cleaning power enables the neutral pH composition to secure emulsifying power and cleaning power equivalent to or higher than that of alkali pH composition including builders, and thus, it does not irritate the skin but has excellent emulsifying power and cleaning power for kitchen and floor and bathroom. The present invention has been completed which is a new liquid detergent composition which can be widely used as a detergent.

The present invention is directed to a new liquid detergent composition which necessarily comprises one or more anionic surfactants and comprises an excess salt, including a nonionic or amphoteric surfactant or mixtures thereof.

First of all, as the anionic surfactant used in the present invention, a water-soluble surfactant having a hydrophilic portion composed of sulfonate and sulfate groups and a hydrophobic portion having 8 to 26 carbon atoms, preferably 10 to 18 carbon atoms, is suitable. The minor moiety consists of alkyl, acyl, alkenyl groups having 8 to 22 carbon atoms. Such surfactants are generally used in the form of water-soluble salts, wherein the cations that form the salt are sodium, potassium, ammonium, magnesium salts or mono-, di-, tri-alkanol ammonium salts, preferably potassium, sodium, ammonium salts. These anionic surfactants are also used as mixtures of one or more different types, in particular sulfonate and sulfate types, as in the general case of dishwashing detergents.

These anionic surfactants used in the present invention serves to improve the cleaning power, emulsifying power of the composition, which will be described in more detail as follows.

Sulfonate-based surfactants are well-known higher alkyl aromatic sulfonates which are higher alkylbenzenesulfos having a straight or branched chain alkyl group having 9 to 18, preferably 9 or 10 to 15 or 16 carbon atoms. Nates, alkyl toluenesulfonates having 8 to 15 carbon atoms and alkylphenol sulfonates having 8 to 15 carbon atoms are suitable.

Other suitable anionic surfactants include long chain alkenes sulfonates, long chain hydroxyalkanesulfonates and olefin sulfonates comprising a mixture of the two. Such olefin sulfonate surfactants are 8 to 25 carbon atoms of sulfur trioxide and the formula R ₁ CH = CHR ₂ (R ₁ is a higher alkyl group having 6 to 23 carbon atoms and R ₂ is alkyl having 1 to 17 carbon atoms). It can be prepared by a known method in which a mixture of sultone and alkene sulphonic acid is formed by reaction with a long chain olefin of dogs, preferably 12 to 21, and then the sulfone is replaced with a sulfonate. Among these olefin sulfonates, sulfonated alpha olefins having 9 to 18 carbon atoms, preferably 12 to 16 carbon atoms, are suitable.

Useful anionic surfactants are also paraffin sulfonates having 10 to 20 carbon atoms, preferably 9 to 18 carbon atoms, more preferably 12 to 17 carbon atoms. Primary paraffin sulfonates are made by the reaction of long chain alpha olefins with bisulfite. Patents for paraffin sulfonates in which sulfonate groups are distributed along paraffin chains are described in US Pat. Nos. 2,503,280; 2,507,088; 3,260,744 and 3,372,188 and German Patent No. 735,096.

In addition, as the sulfate-based anionic surfactant, an alkyl sulfate having 8 to 18 carbon atoms and a formula R ₃ (OC ₂ H ₄ ) _n OSO ₃ M (where R ₃ is an alkyl group having 8 to 18 carbon atoms, n is 1 to 1) 22, preferably having a value from 1 to 5, M is an alkyl polyethoxysulfate of sodium, potassium, ammonium, magnesium, mono-, di-, tri-ethanol ammonium salts). Alkyl sulfates are obtained by sulphating alcohols obtained by reducing glycerides in coconut oil or tallow or mixtures thereof and neutralizing the resulting organic sulfonic acid esters. Alkyl polyethoxy sulfates are obtained by sulphating the condensation reaction product of ethylene oxide with alkanols having 8 to 18 carbon atoms and neutralizing the resultant. Alkyl polyethoxy sulfates vary depending on the number of carbon atoms of the alcohol and the number of moles of ethylene oxide reacting with one mole of alcohol. Preferred alkyl sulfates and alkyl polyethoxy sulfates are those having 10 to 16 carbon atoms in the alcohol, such as laruyl sulfate sodium salt, myristyl sulfate sodium salt and the like.

Among these anionic surfactants, preferred surfactants used in the present invention are paraffin or alkane sulfonates having 12 to 16 carbon atoms, and alkyl polyethoxy sulfates having 12 to 16 carbon atoms and 1 to 5 moles of ethylene oxide groups. . Particularly preferred surfactants are alkanesulfonates having 12 to 14 carbon atoms and alkyl polyethylene sulfates containing 12 to 14 carbon atoms and containing 1 to 3 moles of ethylene oxide.

The amount of the surfactant used in the present invention is 10 to 40% by weight of the total composition, and the proportion of the anionic surfactant in the total amount of the surfactant is 50 to 95%, preferably 50 to 90%, more preferably 5 To 80%, particularly preferably the alkyl sulfate, alkyl ethoxy sulfate, having a value between 50 and 90%, preferably between 50 and 85%, more preferably between 50 and 80%. In the composition having a value of 50% or less of such anionic surfactant, emulsifying power and detergency are poor, and the same is true in a composition having 95% or more.

Next, in the present invention, a nonionic surfactant is used to increase cleaning power and increase bubble stability. Representative of such nonionic surfactants are water-soluble aliphatic or alkylaromatic hydrophobic moieties and ethylene oxide hydrophilic moieties, and the molar number of ethylene oxide in straight or branched hydrophobic moieties having 8 to 18 carbon atoms is preferably 2 to 30, preferably Those which are 2 to 10 are suitable.

Polar nonionic surfactants that may be used in addition to the aforementioned nonpolar nonionic surfactants include those having semi-polar bonds, such as N → O and P → O, between the two elements present in the hydrophilic region. . In this structure, there is a separation of charges between molecules that are directly bonded, but they are not charged and dissociated into ions as a whole. Such polar nonionic surfactants include aliphatic amine oxides of the formula R ₁ R ₂ R ₃ N → O. Wherein R ₁ is an alkyl group having 10 to 16 carbon atoms and R ₂ , R ₃ are methyl, ethyl, propyl, ethanol, propanol radicals. Preferred amine oxides are alkyl dimethyl and dihydroxyethyl amineoxide having 10 to 16 carbon atoms. Other usable surfactants include aliphatic phosphine oxides of formula R ₄ R ₅ R ₆ P → O. Wherein R ₄ is an alkyl group having 10 to 18 carbon atoms, and R ₅ , R ₆ are alkyl, monohydroxyalkyl radicals having 1 to 3 carbon atoms.

Other nonionic surfactants used are fatty acid ethanol amides having intramolecular amide bonds. It has a structure of RCON (CH ₂ CH ₂ OH) n where R is an alkyl group having 8 to 22 carbon atoms and n has a value of 1 or 2.

The proportion of the nonionic surfactant in the total amount of the surfactant used in the present invention is 5 to 50%, preferably 5 to 45%, more preferably 5 to 40%. Particularly preferably used alkyl amine oxides, fatty acid ethanolamides have a value between 5 and 50%, preferably between 5 and 40% and more preferably between 5 and 30%. When the ratio of the nonionic surfactant is 5% or less, the effect of increasing the foaming power is insignificant, and in the 50% moving composition, the overall detergency is poor.

Next, the amphoteric surfactants used in the present invention include partial acidic portions of carboxyl, sulfonic acid, sulfonic acid semiestrer, phosphonic acid, and phosphoric acid in the molecule. (partial acid group) with primary, secondary, tertiary and quaternary ammonium groups as base. Amphoteric surfactants with quaternary ammonium groups are betaines or zwitterionic surfactants.

These amphoteric surfactants are mixed with anionic surfactants to further improve the cleaning power. Particularly, some of the linear groups have 8 to 18 carbon atoms and the other are carboxy, sulfonate and sulfate groups. Derivatives of linear quaternary ammonium compounds. Representatives include alkyl dimethyl sulfobetaine (3- (hexadecyl-N, N-dimethylammonio) -propane sulfonate, 3- (N-tallowalkyl-N, N-dimethylammonio) -2-hydride Hydroxypropanesulfonate, 3- (N-hexadecyl-N, N-bis- (2-hydroxyethylammonio) -2-hydroxypropylsulfate, 3- (N-cocosaalkyl-N, N-bis -(2,3-dihydroxypropylammonio) -propane sulfonate), alkyl dimethyl betaine (N-tetradecyl-N, N-dimethylammonoacetate, N-hexadecyl-N, N-bis- ( 2,3-dihydroxypropyl) -ammonio acetate), alkyl amido betaine (C12-C18-acyl amidopropyl dimethyl ammonium betaine), cocoampocarboxyglycinate (N-coco-acylamidoethyl -N, N-bis- (carboxymethyl) -ammonioethanol) are preferably used.

The proportion of amphoteric surfactant in the total amount of the surfactant alone used in the present invention has a value between 5 and 50%, preferably between 5 and 45%, more preferably between 5 and 40%. In the composition having a ratio of the amphoteric surfactant of 5% or less, the effect of improving the cleaning power is insignificant, and in the composition having 50% or more, the overall cleaning power is poor.

The present invention includes an excess salt in order to further improve the emulsifying power and the cleaning power in the above surfactant combination. Suitable salts used herein are sodium chloride, ammonium chloride, potassium chloride, lithium chloride, bromosodium, bromoammonium, bromopotassium, bromolithium and more preferably sodium chloride, ammonium chloride.

The amount of salt used herein is 0.1 to 50% by weight based on the total amount of the composition, the ratio of 0.01: 1 to 10: 1 based on the total amount of the surfactant, preferably 0.1: 1 to 5: 1. If the amount of the salt is 0.1% by weight or less, the improvement in the cleaning power and the emulsifying power by addition of the salt is insignificant, and the same is true in the case of 40% by weight or more.

Generally, salts are generally used to increase viscosity in detergent compositions, but in the present invention are used to improve emulsification and detergency in addition to the conventional thickener role. The use of such salts ensures emulsification and detergency similar to alkaline pH conditions, including builders, even at neutral pH conditions. A more detailed description thereof will be described in more detail in the following examples.

Acidic agents used for pH control include hydrochloric acid, sulfuric acid, disulfates in alkali gold, aminosulfuric acid, phosphoric acid or other acids of phosphorus, in particular anhydrous or salts of phosphorus, acetic acid amide, and phosphoric acid. Amide or phosphoric anhydride, citric acid, tartaric acid, lactic acid and the like. Organic or inorganic compounds such as alkanolamines or ammonia may be added as basic agents.

Suitable fat solvents in the present invention are commercial terpene compounds characterized by citrus fruit flavors, such as terpene hydrocarbons, such as limonne and terpene alcohol. Glycol ether, which is a pine oil or has a high molecular weight of 200,000 to 4,000,000, has not only its own function of controlling viscosity, but also aids in the emulsification and contamination of fats in actual use. Used in combination with other compositions shows improved detergency against hydrophobic contamination. The polyethylene glycol used previously has the formula HO- (CH ₂ -CH ₂ -O) _n -H and n has a value of 4,800 to 64,600. The fatty solvent itself is an oil component, solubilizing in a surfactant, so that a large amount of contamination is more easily solubilized into the surfactant solution.

In addition to the above components, the additives used in the present invention include dyes, preservatives, perfume, etc., and the rest is ion-exchanged water.

The present invention having the above components as its constituents can be used as a multipurpose cleaner by showing improved emulsification and detergency at pH neutral to grease or oily contamination compared to conventional detergent formulations. This performance is described in more detail by the following examples, but these examples are only for the understanding of the present invention, but do not limit the scope of the present invention in any sense.

Example 1

In order to know the effect of each surfactant in the surfactant formulation, the detergent composition was tested by combining the detergent composition according to the composition shown in Table 1 and the results are shown in Table 1 below.

The cleaning power is according to the KS M 2716 method (liners method). The composition of the soil used in the cleaning test was 10 g each of soybean oil and tallow, 0.1 g oil red (dye), 0.25 g glyceryl monooleate (surfactant), and 60 ml chloroform (solvent). . The contamination was prepared and uniformly coated on a glass specimen (2.5 cm x 7.5 cm), and then the detergent concentration was 0.04% by weight at 100 rpm in a stirred mixed detergent tester (terg-o-tomenter, US Testing Co., Inc.). The amount of contamination remaining after washing for 3 minutes was measured to determine the decontamination rate, that is, the cleaning power [cleaning force (decontamination rate) = ((initial contamination amount-contamination amount after cleaning) / initial contamination amount) × 100].

In Table 1, pH adjusters, fat solvents, dyes, preservatives, flavors, and ionized water added in addition to the surfactants and salts were omitted unless otherwise noted, and separately mentioned when necessary. The same applies to the following examples. The figures mentioned in the tables below are in weight percent relative to the total amount of the detergent composition, unless otherwise noted.

TABLE 1

As shown in Table 1 above, in the combination of nonionic or amphoteric surfactants without anionicity (1-A), the cleaning power was 40%, and when only anionic was used alone (1-B), it was 45% but anionic When surfactants were mixed with nonionic or amphoteric surfactants (1-D), they showed improved cleaning power (50%). However, when the amount of the nonionic or amphoteric surfactant is too small (1-C), the effect by these is almost insignificant. In addition, when the nonionic or amphoteric surfactant is present in excess of the anionic (1-D), when the nonionic or amphoteric surfactant is present in the range between 20: 1 to 1: 2 compared to the anionic and nonionic or amphoteric (1-E) More improved cleaning power.

The above results show that when anionic surfactants and nonionic or amphoteric surfactants are used together, the cleaning power is improved than when they are used alone, and the cleaning power is further improved when used at an appropriate mixing ratio.

Example 2

In order to obtain more improved cleaning power in the suitable detergent composition obtained in Table 1, the detergent was formulated according to the salt concentrations of Table 2 to test the cleaning power and the results are shown in Table 2 below.

TABLE 2

As shown in Table 2, it can be seen that the washing power increases as the concentration of the salt increases. From these results, it can be seen that an improved detergency can be obtained when an excess salt is present in the surfactant formulation.

The increase in detergency with the increase in the concentration of these salts is explained for the sake of understanding, since the interfacial tension decreases rapidly as the concentration of the salt increases, so that oily contamination decreases more easily and quickly. Under normal surfactant conditions, the interfacial tension for oily contamination is around 1 dynes / cm, so oily contamination is not easily mixed with the surfactant solution, but if the interface tension decreases rapidly to ~ 10 ^-3 dynes / cm with increasing salt concentration, This easily mixes into the surfactant solution and consequently the contamination is easily removed. This is particularly important for kitchen, floor and bathroom detergents where the removal of oily contamination is a problem.

Example 3

In order to determine the applicability of the prescriptions obtained in Tables 1 and 2 as dishwashing detergents, the cleaning power at neutral pH was compared with conventional kitchen products (3-C), and the conventional floor and bathroom was checked to confirm the increased cleaning power. Compared with the detergent (3-B), the results are shown in Table 3 below.

TABLE 3

As shown in Table 3, the new prescription (3-A) containing an excess salt shows the same cleaning power as the conventional multi-purpose detergent (3-B) having an alkaline pH value while having a neutral pH value. Compared to detergent (3-C), it does not show a significant increase in cleaning power, but even better. That is, it shows the same or improved cleaning power regardless of pH compared to the existing products of various uses.

From these results, the present invention shows an improved cleaning power compared to the cleaning power of the conventional kitchen detergent at neutral pH, which is advantageous when applied to the kitchen detergent which should maintain the neutral pH due to the irritation to the skin. It is also shown that it is suitable in terms of detergency in furnace applications.

Example 4

In addition to the suitability as a kitchen detergent of Example 3, in order to confirm the excellent emulsification power for the removal of a lot of contamination required to meet the requirements as a multipurpose detergent for the purpose of the present invention by comparing the emulsifying power with the existing multi-purpose detergent and the results are shown in Table 4 Shown in

The emulsification test was carried out by dipping glass specimens coated with 0.05 ml of oily contamination (9.9 g of soybean oil, 0.1 g of cholesterol) in 50 ml of 0.1 wt% of surfactant (excluding salt concentration), and then leaving it as it is to measure the time required for the entire solution to become cloudy. It is.

TABLE 4

As can be seen in Table 4, the new prescription (4-A) shows a significantly improved emulsification power compared to the conventional kitchen detergent (4-C) at neutral pH, and has a conventional basic pH and floor detergent (4 It shows excellent emulsification power compared to -B), so it can be applied as a detergent for floor and bathroom.

Example 5

In the case of floor and bathroom cleaners, a large amount of decontamination is required, and for this purpose, a fat solvent is used to help emulsify fats and remove contamination. In order to see the effect, the cleaning power according to the presence of a fatty solvent is shown in Table 5 below.

TABLE 5

As shown in Table 5, the addition of the fatty solvent does not show a significant difference in the cleaning power. However, since the fat solvent itself is solubilized in the surfactant, if the amount of contamination in actual use is large, the contamination is more easily solubilized and cannot be resorbed again if the contamination is dispersed into the surfactant solution. It can be removed (US Pat. No. 4,797,231), which is useful for floor and bathroom detergents.

Based on the above results, the new liquid detergent composition according to the present invention shows improved emulsification and detergency of the existing floor and bathroom detergent levels even in the neutral pH range, and thus, a large amount of kitchen detergent or a large amount of detergent which is required to be washed under the neutral pH conditions. It is expected to be applied as a versatile detergent that can be used for both bathroom and floor detergent applications requiring good emulsification and detergency for decontamination.

Claims (2)

In detergent compositions containing anionic surfactants, nonionic surfactants or amphoteric surfactants and salts, the anionic surfactants are C ₁₂ -C ₁₄ alkylsulfate sodium or ammonium salts, C ₁₂ -C ₁₄ alkylbenzenesulfonate sodium Salt, C ₁₂ -C ₁₄ alkyl- (ethoxy) ₂ -sulfate sodium salt or a mixture thereof and an anionic surfactant content of 50 to 95% by weight, wherein the nonionic surfactant is lauryldimethylamineoxide or C ₁₂ -fatty acid diethanolamide, wherein the amphoteric surfactant is cocoampocarboxaglycinate, the content of nonionic surfactant or amphoteric surfactant is 5-50% by weight, and the total amount of the surfactants is the total composition 10 to 40% by weight relative to the total amount, containing 0.1 to 50% by weight of the total amount of the total composition of the ammonium chloride as a salt, In a weight ratio of 1: 0.01 to 1: 5, and comprises a pH adjusting agent or a fat solvent, as an additive in addition, multi-purpose liquid detergent composition characterized in that the whole of the composition, pH 5 to 11. The multipurpose use according to claim 1, wherein the pH adjusting agent is one or more selected from hydrochloric acid, sulfuric acid, bisulfate salt of alkali metal, amino sulfuric acid, phosphoric acid, acetic acid amide, citric acid, tartaric acid, and lactic acid, and the fatty solvent is polyethylene glycol (molecular weight 20,000). Liquid detergent composition.