JP2002194388A - Liquid detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid detergent composition having moderate viscosity even if being high in surfactant concentration, highly miscible with water, and exhibiting high detergency effect and its sustainability in a washing method of infiltrating each a small amount of water and a detergent liquid into a flexible absorber such as a sponge. SOLUTION: This liquid detergent composition comprises 25-55 wt.% of a polyoxyalkylene 8-16C alkyl ether sulfate salt, a total of 30-60 wt.% of surfactants and 1-10 wt.% of a water-miscible organic solvent (provided that ethanol is at <=5 wt.% in the composition) and has a viscosity of 400-1,000 mPa.s at 20 deg.C; wherein surfactant(s) having branched-chain alkyl group account for 20-80 wt.% of the total surfactant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a liquid detergent composition.

[0002]

2. Description of the Related Art As consumers are becoming more and more conscious of the environment, efforts are being made to reduce the amount of waste in detergents, and to increase the concentration of compositions. Techniques have been developed to reduce the amount of waste by reducing the amount of cleaning agent used at one time and reducing the size of containers.

[0003] In addition to the cleaning performance, the cleaning agent is required to have a long-lasting detergency. For example, when washing dishes by hand washing, it is preferable that the number of dishes that can be washed by one impregnation after impregnating the flexible absorber with a detergent is larger. Regarding the dishwashing method, use an aqueous solution obtained by diluting a cleaning agent with water, and rub and wash with a flexible absorber such as a sponge or towel while contacting an object to be washed such as tableware, or a method using a washing solution and a small amount of water. There is a method of scrubbing tableware and the like using a flexible absorbent material directly impregnated with, and the latter method is generally often used.

[0004] On the other hand, polyoxyalkylene alkyl ether sulfates have high detergency and low irritation to the skin. Therefore, dishwashing detergents for hand washing (hereinafter abbreviated as dishwashing detergents) and body washing agents are used. Used for However, when the concentration of the surfactant in the composition containing the polyoxyalkylene alkyl ether sulfate is increased, the viscosity of the composition is significantly increased. As a method for solving this, it is conceivable to use a solvent or a hydrotrope agent in combination, but there is a problem that the effect is low in a composition containing a large amount of polyoxyalkylene alkyl ether sulfate.

JP-A-53-64209 discloses a highly concentrated liquid detergent composition containing a secondary alcohol ethoxylate sulfate, but the effect of suppressing an increase in viscosity is still satisfactory. In addition, the cleaning effect is not sustained in a method in which a cleaning liquid and a small amount of water are impregnated into a flexible absorber and directly rubbed on an object to be cleaned such as tableware.

Japanese Patent Application Laid-Open No. Sho 56-141400 discloses a composition containing an amine oxide having a branched chain alkyl group. Cause an increase.

Japanese Unexamined Patent Publication No. 11-513067 discloses a technique relating to a dishwashing detergent in which a washing solution having a high surfactant concentration is dissolved in water without gelling. This technique is to prevent the detergent from gelling at a high surfactant concentration by blending a gelling inhibitor. However, the composition disclosed in this publication cannot wash many dishes when the flexible absorbent is impregnated with a small amount of water and a washing liquid and washed.

[0008] Accordingly, an object of the present invention is to provide an appropriate viscosity even when the concentration of a surfactant is high, which not only has excellent solubility when diluted with water and used, but also has a high detergency and a detergency. An object of the present invention is to provide a liquid detergent composition having excellent durability.

[0009]

SUMMARY OF THE INVENTION The present invention relates to a method for producing a compound having 8 to 1 carbon atoms.
6 to 25% by weight of a polyoxyalkylene alkyl ether sulfate having an alkyl group, a surfactant in a total amount of 30 to 60% by weight, and a water-soluble organic solvent in an amount of 1 to 10% by weight (excluding ethanol). Does not exceed 5% by weight in the composition) and has a viscosity at 20 ° C. of 400
Provided is a liquid detergent composition having a liquid detergent composition having a branched chain alkyl group content of 20 to 80% by weight based on the total weight of the surfactant.

[0010]

DETAILED DESCRIPTION OF THE INVENTION The composition of the present invention has 10 to 10 carbon atoms.
25 to 55% by weight, preferably 25 to 50% by weight of a polyoxyalkylene alkyl ether sulfate having 16 alkyl groups, and the total amount of surfactants;
Preferably, the total amount of the surfactant having an alkyl group having 8 to 16 carbon atoms is 30 to 60% by weight, preferably 35 to 60%.
It is a liquid detergent composition based on polyoxyalkylene alkyl ether sulfate, which is in weight percent. Such compositions have high detergency and long lasting properties and have low skin irritation.

The composition of the present invention preferably contains 50 to 100% by weight, preferably 55 to 95% by weight, of the polyoxyalkylene alkyl ether sulfate based on the total weight of the surfactant in the composition. More preferably, 60-
90% by weight is more preferred.

The alkyl group of the polyoxyalkylene alkyl ether sulfate has 8 to 16 carbon atoms.
It is preferably from 10 to 16, and may be linear or branched. The alkylene oxide is preferably ethylene oxide, and the average number of moles of ethylene oxide added is preferably 1.5 to 6.0, more preferably 1.6 to 4.0, and particularly preferably 2.0 to 3.5.

In the present invention, the surfactant having a branched alkyl group is used in an amount of from 20 to 20% by weight based on the total weight of the surfactant.
The content is 80% by weight, preferably 20 to 60% by weight, particularly preferably 20 to 50% by weight. Here, the branched chain alkyl group is an alkyl group having at least one, preferably 1 to 5 carbon atoms to which 3 or 4 carbon atoms are bonded. Moreover, the total carbon number of the branched alkyl group is 8 to
16, more preferably 10 to 16.

As the surfactant having a branched alkyl group used in the present invention, a surfactant derived from an alcohol or a fatty acid obtained by an oxo reaction or a Guerbet reaction is preferable. In the oxo reaction, a methyl-branched primary alcohol or a methyl-branched fatty acid obtained by reacting a 1-alkene having 8 to 15 carbon atoms with carbon monoxide can be obtained. It is also possible to obtain a polymethyl-branched alcohol or a polymethyl-branched fatty acid obtained by reacting diisobutylene, triisobutylene or tetraisobutylene with carbon monoxide. In the Guerbet reaction, two
A primary alcohol having an alkyl group branched at the position can be obtained. It is also possible to cause the Guerbet reaction by simultaneously causing the dehydrogenation reaction and the hydrogenation reaction of the alcohol using a Ni catalyst or the like.

In the present invention, a surfactant obtained by further derivatizing such an alcohol or fatty acid is used. Specifically, a branched-chain alkyl sulfate obtained by sulfating the alcohol obtained above with SO ₃ or chlorosulfonic acid, etc., ethylene oxide (hereinafter referred to as EO) and / or propylene oxide (hereinafter referred to as EO) , PO)
To obtain a polyoxyethylene (and / or propylene) branched alkyl ether. Further, a polyoxyethylene (and / or propylene) branched alkyl ether sulfate salt obtained by sulfating this with SO ₃ or chlorosulfonic acid can also be used.

The derivative of a branched chain fatty acid is obtained by subjecting an amidation reaction product with dimethylaminopropylamine to a quaternization reaction using an alkylating agent such as an alkyl chloride, an alkyl bromide, a dialkyl sulfate or an alkylene oxide. The resulting quaternary ammonium salt or an amine oxide compound oxidized with an oxidizing agent such as hydrogen peroxide for the amidation reaction product can be used.

In the present invention, among these, the following (I) to
A branched alkyl surfactant selected from (IV) is preferable, and (I), (II) and (IV) are particularly preferable. (I) a branched alkyl primary alcohol having 8 to 16 carbon atoms in the total alkyl group and 7 to 15 carbon atoms in the longest linear alkyl chain, and having 1 to 5 methyl or ethyl groups branched A polyoxyethylene (and / or propylene) branched alkyl ether (II) having an average of 4 to 50, preferably 5 to 20 EO and / or PO added thereto, wherein all alkyl groups have 8 to 16 carbon atoms and the longest straight chain 7 carbon atoms in the alkyl chain
EO and / or PO, preferably EO, on the average of 1.5 to 6.0, more preferably 1. 0 to 15 in a branched alkyl primary alcohol having 1 to 5 methyl or ethyl groups. 6-4.0, particularly preferably 2.0-3.5
The polyoxyethylene (and / or propylene) branched alkyl ether sulfate ester sulfated with SO ₃ or chlorosulfonic acid is further added to the molar addition product, (II
I) a branched alkyl primary alcohol having 8 to 16 carbon atoms in the total alkyl group, 7 to 15 carbon atoms in the longest straight chain alkyl chain, and 1 to 5 methyl or ethyl groups branched; A branched alkyl sulfate salt sulfated with SO ₃ or chlorosulfonic acid, (IV) the total alkyl group has 8 to 16 carbon atoms, the longest linear alkyl chain has 7 to 15 carbon atoms, and a methyl group or Alkanoylaminopropyl- using a branched chain fatty acid having 1 to 5 ethyl groups as a raw material
N, N-dimethylamine oxide.

When the compound of (II) and / or (III) is used, the counter ion is a sodium salt, a potassium salt,
At least one selected from magnesium salts is desirable.

In the present invention, it is preferable to use a linear surfactant in addition to the above-mentioned branched surfactant. As the linear surfactant, particularly, an alkyl group having 10 to 1 carbon atoms.
6, preferably 10 to 14 carbon atoms, the average degree of condensation of the alkylene oxide is preferably 1.5 to 6.0, more preferably 1.6 to 4.0, and particularly preferably 2.0 to 3.5. An oxyalkylene alkyl ether sulfate salt, an amine oxide compound represented by the general formula (i), and at least one nonionic surfactant selected from the following general formulas (ii) to (iv) may be blended. preferable.

[0020]

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Wherein R ¹ is a straight-chain alkyl group or alkenyl group having 8 to 16, preferably 10 to 16, and particularly preferably 10 to 14, carbon atoms, and R ³ and R ^{4 each} have 1 to 3 carbon atoms.
Is an alkyl group or a hydroxyalkyl group. R ² is an alkylene group having 1 to 5, preferably 2 or 3, carbon atoms. A represents -COO-, -CONH-, -OCO-, -N
A group selected from HCO- and -O-, wherein r is 0 or 1
Is the number of ].

R ⁵ —O (EO) _n H (ii) wherein R ⁵ is an average of 8 to 16, preferably 10 to 10 carbon atoms
Sixteen straight-chain alkyl groups. EO is ethylene oxide, and n is 5 to 20 as an average number of added moles. R ⁶ —O [(EO) _p / (PO) _q ] H (iii) wherein R ⁶ has an average carbon number of 8 to 16, preferably 10 to 10.
Sixteen straight-chain alkyl groups. EO indicates ethylene oxide, and PO indicates propylene oxide. p is 5-1
5, q is 1 to 5. EO and PO may be added randomly, or PO may be added after EO is added, or vice versa. ] _{^{R 7 - (OR 8) x}} G y (iv) wherein, R ⁷ is an alkyl group having 8 to 16 carbon atoms, straight-chain alkenyl group, or alkylphenyl group, R ⁸ is 2 carbon atoms
To 4 alkenyl groups, G is a residue derived from a reducing sugar having 5 or 6 carbon atoms, x is an average number of 0 to 6, and y is an average value of 1 to 1.
Indicates the number of 0. ].

In the present invention, the branched and straight chain type surfactants are mixed and used. However, from the viewpoint of obtaining a cleaning effect and an appropriate viscosity, all the amine oxides including the branched chain and the straight chain are used in the composition. Preferably, the composition contains 1 to 10% by weight, particularly 3 to 9% by weight, and the total content of nonionic surfactants is 1 to 20% by weight, particularly 3 to 15% by weight in the composition. . Further, from the viewpoint that an appropriate viscosity is obtained, all polyoxyalkylene alkyl ether sulfates /
The weight ratio of all amine oxides is preferably 2/1 to 10
/ 1, particularly preferably 3/1 to 10/1.

In the present invention, a surfactant other than the above-mentioned surfactants can be blended, but it is important that the desired viscosity is not impaired. As the anionic surfactant, a linear alkylbenzene sulfonate, an α-sulfofatty acid ester salt, an α-olefin sulfonate, or an alkane sulfonate which is usually used in a liquid detergent may be blended. The content of the ionic surfactant is preferably 5% by weight or less, and more preferably 3% by weight or less in order to satisfy the above properties. Carbobetaine and sulfobetaine can be blended as the amphoteric surfactant. The blending amount of these amphoteric surfactants is preferably 5% by weight or less.
It is more preferably at most 3% by weight.

The composition of the present invention further comprises an alkali metal cation and / or
Or it is desirable to contain an alkaline earth metal cation preferably in an amount of 2 to 10% by weight, more preferably 3 to 8% by weight. Sodium ions and potassium ions are preferred as alkali metal cations, and magnesium ions are preferred as alkaline earth metals. In the present invention, the magnesium ion is preferably 0.2 to 2% by weight,
More preferably, it is preferably blended at a concentration of 0.3 to 1.5% by weight. In the present invention, the amount of the cation includes the counter ion of the anionic surfactant and all the components incorporated from other components, and when the content is insufficient, sodium sulfate, potassium sulfate, magnesium sulfate, sodium chloride And at least one water-soluble inorganic salt selected from potassium chloride, magnesium chloride, sodium hydroxide, potassium hydroxide, and magnesium hydroxide. When the amount of these cations is too large, it is preferable to remove salts using a technique such as electrodialysis. The amount of such inorganic cations can be determined, for example, by quantifying the entire composition by a conventional inorganic analysis method such as an atomic absorption method.

In the present invention, a water-soluble organic solvent is blended to adjust the solubility in water and the desired viscosity. Examples of the water-soluble organic solvent include (1) a monohydric alcohol having 1 to 5 carbon atoms,
(2) a polyhydric alcohol having 4 to 12 carbon atoms; (3) a compound represented by the following general formula (v); (4) a compound represented by the following general formula (vi); General formula (vii)
The compound represented by is preferred.

[0027]

Embedded image

[In the formula, R ⁹ and R ¹⁰ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a benzyl group, and when both R ⁹ and R ¹⁰ are hydrogen atoms, except. s represents a number from 0 to 10, and t represents a number from 0 to 10, except when both s and t are 0. R ¹¹ and R ¹² represent an alkyl group having 1 to 3 carbon atoms. R ¹³ represents an alkyl group having 1 to 8 carbon atoms. ].

Examples of the (1) monohydric alcohol having 2 to 5 carbon atoms include ethanol, propyl alcohol and isopropyl alcohol. By incorporating these lower alcohols, the stability of the system at low temperatures can be further improved.

The polyhydric alcohols having 4 to 12 carbon atoms (2) include isoprene glycol, 2,2,4-trimethyl-1,3-pentanediol, 1,8-octanediol and 1,9-nonanediol. , Ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin and the like.

The compound (3) has a carbon number of 1 to ⁹ when R ⁹ and R ¹⁰ are alkyl groups in the general formula (v).
4 is particularly preferred. Further, in the general formula (v), EO and P
The average number of moles of O, s and t, are each a number from 0 to 10 (except when both s and t are 0),
The order of addition is not particularly limited, and may be random addition. Specific examples of the compound (3) include ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether, Polyoxyethylene (p = 2
3) polyoxypropylene (p = 2 to 3) glycol dimethyl ether (p indicates the average number of moles added), polyoxyethylene (p = 3) glycol phenyl ether,
Phenyl carbitol, phenyl cellosolve, benzyl carbitol and the like can be mentioned. Among these, propylene glycol monomethyl ether, diethylene glycol monobutyl ether, and polyoxyethylene (p = 1 to 4) glycol phenyl ether are preferred from the viewpoints of detergency and usability.

The compound (4) includes 1,3-
Dimethyl-2-imidazolidinone, 1,3-diethyl-
2-imidazolidinone is exemplified as being preferred,
As the compound of (5), an alkyl glyceryl ether compound is exemplified as a preferable compound, and among them, a compound in which R ¹³ is an alkyl group having 3 to 8 carbon atoms is preferable.

Of these, the water-soluble organic solvents (1), (2), (3) and (5) are preferred in order to satisfy the properties of the present invention. In particular, ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, A water-soluble organic solvent selected from diethylene glycol, dipropylene glycol, glycerin, isoprene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, pentyl glyceryl ether, and octyl glyceryl ether is preferred.

In the composition of the present invention, such a water-soluble organic solvent is blended in an amount of 1 to 10% by weight, preferably 2 to 8% by weight from the viewpoint of solubility. It preferably does not exceed 5% by weight, preferably 3% by weight in the composition. If you mix a lot of water-soluble organic solvents,
Not only the viscosity is lowered but also the fluidity is increased, so that crystals are likely to be generated at a low temperature, or when left at room temperature, the water-soluble organic solvent volatilizes from the surface, which tends to form a film. These water-soluble organic solvents are effective components for lowering the viscosity. However, in the present invention, when the water-soluble organic solvent is blended, the viscosity of the liquid detergent composition is 400 m.
It is adjusted appropriately so as not to be less than P · s. Viscosity 4
If the amount is less than 00 mP · s, the effect of maintaining the detergency cannot be obtained.

It is preferable that the composition of the present invention further contains a hydrotroping agent in view of storage stability, viscosity adjustment and viscosity stability (the viscosity does not change with time). As the hydrotroping agent, toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid and their sodium, potassium or magnesium salts are preferred, and p-toluenesulfonic acid and its salts are particularly preferred.

The composition of the present invention preferably contains 0.5 to 5% by weight, particularly preferably 1 to 5% by weight of a hydrotrope.

The composition of the present invention is in the form of an aqueous solution containing the above components and water, and the content of water is from 20 to 60% by weight, preferably from 30 to 60% by weight, from the viewpoint of obtaining an appropriate viscosity.
It is 60% by weight, more preferably 40-60% by weight, particularly preferably 45-55% by weight. In addition, 2 of the composition
PH at 0 ° C. is 6-8, preferably 6.5-7.5.
Is preferred from the viewpoint of storage stability and safety on the skin. Inorganic acids such as hydrochloric acid and sulfuric acid as pH adjusters,
Acid agents such as citric acid, succinic acid, malic acid, fumaric acid, tartaric acid, malonic acid, maleic acid and other organic acids, sodium hydroxide, potassium hydroxide, ammonia and derivatives thereof, monoethanolamine, diethanolamine, triethanol It is preferable to use an alkali agent such as sodium carbonate, potassium carbonate or the like alone or in combination with an amine salt such as an amine, and in particular, an acid selected from hydrochloric acid, sulfuric acid and citric acid and selected from sodium hydroxide and potassium hydroxide. It is preferable to use an alkali agent.

The liquid detergent composition of the present invention has a viscosity at 20 ° C. of 400 to 1000 mPa · s, preferably 4 to 1000 mPa · s.
00 to 900 mPa · s, especially 500 to 900 mPa · s
By adjusting the viscosity to such a value, it is possible to enhance the durability of the detergency in a method of directly impregnating and cleaning the flexible absorber. Adjustment of viscosity, in addition to adjusting the type of surfactant having a branched chain and the combination or branching rate of the surfactant, adjust the amount of the hydrotrope, water-soluble organic solvent, water-soluble inorganic salt and water. May be performed.

The viscosity in the present invention is measured as follows. First, a B type viscometer model BM manufactured by TOKIMEC.INC equipped with a rotor of rotor number No. 3 is prepared. The sample is filled in a tall beaker and adjusted to 20 ° C. in a 20 ° C. thermostat. The sample prepared at a constant temperature is set in a viscometer. Rotor speed 3
It is set to 0 r / m, and the viscosity 60 seconds after the start of rotation is defined as the viscosity of the present invention.

The liquid detergent composition of the present invention comprises components generally blended in a liquid detergent such as a fragrance component, a colorant, a dispersant, an abrasive, a germicide / antifungal agent, and the like. Can be blended in a range that does not affect the viscosity.

[0041]

EXAMPLES A cleaning composition was prepared using the components shown in Table 1. The viscosity, persistence of the cleaning effect, and solubility in water of these compositions were evaluated by the following methods. Table 1 shows the results.

<Detergency test>-Adjustment of model dirt Salad oil / tallow is mixed at a weight ratio of 1/1, and 0.1% by weight.
2 g of a model oil stain uniformly mixed with 1% by weight of a dye (Stan Red) was spread evenly on a melamine dish and used as model-contaminated tableware. -Cleaning method and evaluation method A commercially available sponge (gold bird cleaner No. 5005, polyurethane foam) is impregnated with the liquid detergent composition of Table 1 and 15 g of tap water in an amount of 0.44 g of the surfactant. Bubble three times with hand. Using this, the model-contaminated tableware was scrubbed, and the number of dishes that could be cleaned (confirmed by disappearance of the color attached to the tableware) was determined.

<Solubility test> Height 13 mm, width 5 mm,
A circular glass plate having a diameter of 35 mm to which three legs each having a thickness of 2 mm were attached was placed in the center of a 200 ml glass beaker, and 200 ml of ion-exchanged water and Teflon (registered trademark) were used.
Stirrer (length 25 mm, diameter 8 mm)
In a constant temperature water bath equipped with a stirrer until the temperature reached equilibrium. 0.25 ml of the composition, which had been previously equilibrated in a constant temperature water bath at 25 ° C., was gently left still at the center of the upper surface of the glass plate using a syringe. Immediately after injection, rotation speed 10
The mixture was stirred at 00 rpm for 30 minutes. A case where the composition was completely dissolved after 30 minutes was evaluated as ○, and a case where the composition remained on the glass plate and in the liquid was evaluated as ×.

[0044]

[Table 1]

(Note) The symbols in the table represent the following. -A-1: sodium polyoxyalkylene branched alkyl ether sulfate obtained from a compound obtained by adding an average of 2 moles of EO to isotridecanol-a-2: 7 moles of EO was added to isotridecanol on average Nonionic surfactant a-3: N-isononanoylaminopropyl-N, N
-Dimethylamine oxide b-1: sodium polyoxyethylene lauryl ether sulfate (average number of moles of EO added: 2) b-2: alkyl group having 12 carbon atoms / 14 carbon atoms
= 60/40 linear mixed alkyl, alkylglucoside having an average degree of condensation of glucoside of 1 b-3: polyoxyethylene lauryl ether (EO
Average number of moles added 7) b-4: lauryl dimethylamine oxide polypropylene glycol: weight average molecular weight 1200 preservative: Proxel BDN (manufactured by Avicia Co., Ltd.) inorganic cation amount: alkali metal determined by atomic absorption method The amount of cations and / or alkaline earth metal cations. -ES: polyoxyalkylene alkyl ether sulfate salt-pH: Adjusted using 1 / 10N-sulfuric acid aqueous solution or 1 / 10N-sodium hydroxide.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Nobuhiro Nishizawa, 1334 Minato, Wakayama-shi, Wakayama Prefecture, Kao Co., Ltd. (72) Inventor Nobuyuki Ogura 1334, Minato, Minato, Wakayama-shi, Wakayama F-term (reference) 4H003 AB27 AB31 AB46 AC05 AC08 AC15 AC16 AD04 AD05 BA12 DA02 DA17 EA19 EA21 EB04 EB22 ED02 FA02 FA28 FA30 FA32

Claims (1)

[Claims] 1. A polyoxyalkylene alkyl ether sulfate having an alkyl group having 8 to 16 carbon atoms in an amount of 25 to 55% by weight, and a surfactant in a total amount of 30 to 6%.
0% by weight, 1-10% by weight of a water-soluble organic solvent (however, ethanol does not exceed 5% by weight in the composition),
A liquid detergent composition having a viscosity of 400 to 1000 mPa · s at 20 ° C., wherein the ratio of the surfactant having a branched alkyl group to the total weight of the surfactant is 20 to 8
A liquid detergent composition which is 0% by weight.