JP2000096086A - Liquid detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a detergent composition having excellent biodegradability, exhibiting excellent detergency even in the case of a small mechanical force, having excellent feeling of washing finish and also sufficient fluidity at a low temperature, and also giving ensured appearance recovery. SOLUTION: This composition contains following components (a)-(d) and a weight ratio of (a)/(b) is (2/1)-(20/1), (b)/(c) is (1/3)-(4/1) and (c)+(d)}/ (a)+(b)} is (1/5)-(2/1). (a) a nonionic surfactant, (b) a tertiary amine salt- or a quaternary ammonium salt-type cationic surfactant having an ester bond or an amide bond and more than one 12-22C acyl group in one molecule, (c) a terpene, (d) an alcoholic organic solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid detergent composition, and more particularly to a liquid detergent composition, which is excellent in biodegradability, exhibits excellent detergency even when the mechanical strength is small, has a good feeling of washing, and has low-temperature stability. And a liquid detergent composition having excellent appearance restoring property.

[0002]

2. Description of the Related Art In recent years, the concentration of detergents has been increased for the purpose of resource saving, energy saving and space saving, and the consumption of liquid detergents has increased due to the ease of use during use. There is a demand for the development of a liquid detergent having high performance. In addition, in response to the diversification of items to be washed, diversification of washing methods, such as soaking and washing using wool courses and dry mark courses in washing machines, is also progressing in general households. The development of a liquid detergent has been desired.

[0003] Examples of surfactants used in liquid detergents include anionic surfactants, nonionic surfactants, amphoteric surfactants, and cationic surfactants (Detergent and cleaning dictionary: Asakura Shoten, 1990). Published year, 103-1
Page 42). JP-A-8-48993, JP-A-8-48994 and JP-A-8-48994 disclose detergents which exhibit sufficient detergency for washing delicate clothes such as silk products, wool products and fashionable clothes and which have an excellent washing feeling. -48995 discloses a detergent composition comprising a combination of a cationic surfactant, a nonionic surfactant, an amine oxide and a glycol ether-based solvent, wherein a di-long chain alkyl quaternary ammonium salt is used as the cationic surfactant. Has been identified. Di-long chain alkyl quaternary ammonium salts have the property of finishing fabrics and clothing flexibly and have been widely used, but their biodegradability when discharged to the environment is not sufficient. For this reason, alternative compounds have been studied (INFORM, VOL. 5, No. 1,
76-84, 1994). As an alternative compound, a compound having an ester bond or an amide bond in the molecule and one compound in the molecule.
A tertiary amine salt or a quaternary ammonium salt having at least two or more acyl groups having 12 to 22 carbon atoms is exemplified.

[0004]

The conventional di-long chain alkyl quaternary ammonium salt having a problem of biodegradability is changed to an alternative compound having excellent biodegradability, and is used for washing and washing and wool course of a washing machine. It is an object of the present invention to provide a detergent composition which provides satisfactory detergency and excellent washing feeling even under a cleaning condition such as a dry mark course where little or no mechanical force is applied. However, a composition using an alternative compound having excellent biodegradability causes cloudiness and solidification at low temperatures, and a liquid detergent composition which returns to a transparent liquid state even when the temperature is returned to room temperature cannot be obtained.

[0005] The present invention solves the above-mentioned problems, has excellent biodegradability, exhibits excellent detergency even when the mechanical strength is small, has an excellent washing feeling, and has sufficient fluidity even at low temperatures. It is another object of the present invention to provide a detergent composition having a good appearance restoring property.

[0006]

That is, the present invention comprises the following components (a) to (d), and the weight ratio of (a) / (b) is 2/1 to 20/1, (b) / (C) weight ratio is 1 /
3-4 / 1, and {(c) + (d)} / ｛(a) +
(B) A liquid detergent composition characterized in that the weight ratio of｝ is 1/5 to 2/1. (A) Nonionic surfactant (b) Tertiary amine salt or quaternary ammonium salt type cation having an ester bond or an amide bond and having at least one acyl group having 12 to 22 carbon atoms in the molecule Surfactant (c) Terpene (d) Alcohol organic solvent

[0007]

DETAILED DESCRIPTION OF THE INVENTION As the component (a) nonionic surfactant used in the present invention, a commonly used nonionic surfactant can be used. Alkylene alkyl ether, polyoxyalkylene alkenyl ether, polyoxyalkylene fatty acid ester, sucrose ester, polyoxyalkylene sucrose ester, sorbitan ester, polyoxyalkylene sorbitan ester, polyglycerin fatty acid ester, polyoxyalkylene hydrogenated castor oil, alkyl glycoside, etc. No. Polyoxyalkylene alkyl ethers are preferred from the viewpoint of securing sufficient detergency. The oxyalkylene group in the polyoxyalkylene derivative is preferably an oxyethylene group or an oxypropylene group. Although it is possible that the oxyethylene group and the oxypropylene group coexist in the same molecule,
In order to exhibit the performance as the cleaning composition in the present invention, the weight of the oxyethylene group is preferably larger than the weight of the oxypropylene group. These nonionic surfactants are used alone or in combination of two or more. If the amount of the nonionic surfactant used in the present invention in the composition is small, a large amount of the composition must be used for washing, and if the amount is large, the solubility in low-temperature water is high. 10 to 60% by weight
Is preferred.

A tertiary amine salt or quaternary ammonium salt type cation having an ester bond or an amide bond of the component (b) used in the present invention and having at least one acyl group having 12 to 22 carbon atoms in the molecule. As the surfactant, a salt such as an esteramine or an amidoamine generated by a condensation reaction between an amine compound corresponding to each compound and a fatty acid or a quaternary ammonium salt thereof can be used.

As such an amine compound, an amine having two or more alcoholic hydroxyl groups or amino groups in the molecule can be used. Specifically, diethanolamine, methyldiethanolamine, ethyldiethanolamine, triethanolamine Amine, aminoethylethanolamine, aminopropylethanolamine, aminopropylmethylethanolamine, 1,2-
Examples thereof include dihydroxypropyldimethylamine, diethylenetriamine, triethyltetramine, and N-alkylpropylenediamine. Examples of the fatty acid or a methyl ester thereof which gives an ester or an amide by reacting with these amine compounds include coconut oil, palm kernel oil, palm oil, soybean oil, sunflower oil, rapeseed oil, cottonseed oil, castor oil, corn oil, and tall. Fatty acids produced by hydrolyzing oils, beef tallow, lard, fish oil or hardened fats and oils obtained by hydrogenating these fats and oils are exemplified. In addition, simple fatty acids obtained by separating these fatty acids by a method such as distillation can be used,
Specifically, lauric acid, myristic acid, palmitic acid,
Stearic acid, oleic acid, behenic acid, erucic acid and the like, isostearic acid as a semi-synthetic acid, synthetic fatty acids derived from petrochemicals, and methyl esters thereof can also be used. These fatty acids can be used alone or in combination of two or more. It is necessary that the fatty acid used is a fatty acid or a methyl ester having 12 to 22 carbon atoms, but a fatty acid or a methyl ester thereof having 16 to 22 carbon atoms is preferable from the viewpoint of ensuring a sufficient washing feeling.

Specific examples of the acid component forming the salt of the amine compound used in the present invention include sulfuric acid, nitric acid, hydrochloric acid, perchloric acid, phosphoric acid, polyphosphoric acid and the like.

As a method for deriving a quaternary ammonium salt, it is common to quaternize a tertiary amine, specifically, a method of reacting methyl chloride, dimethyl sulfate or diethyl sulfate, or There is a method of reacting an alkylene oxide. Tertiary amine salt or quaternary ammonium salt type cationic surfactant having an ester bond or an amide bond of component (b) used in the present invention and having at least one acyl group having 12 to 22 carbon atoms in the molecule. Specific examples of the quaternary ammonium salt obtained by the reaction of a diester of triethanolamine and hardened tallow fatty acid with dimethyl sulfate or diethyl sulfate, and the quaternary ammonium salt obtained by the reaction of methyl ester of methyl diethanolamine with tallow fatty acid and methyl chloride A quaternary ammonium salt, a quaternary ammonium salt obtained by obtaining a diesteramine salt of methyldiethanolamine and stearic acid by an alkylene oxide, and the like are preferable, and the blending amount of the component (b) in the composition of the present invention is 1 to 10% by weight. Is preferred.

In the composition of the present invention, the weight ratio (a) / (b) of the component (a) to the component (b) is such that, even when the mechanical force is small, excellent detergency is exhibited, and at the same time, the washability is improved. It is particularly important to balance the texture, and the ratio needs to be 2/1 to 20/1, preferably 5/2 to 15/1. If it is less than 2/1, sufficient detergency cannot be obtained, and if it exceeds 20/1, a good texture after washing cannot be obtained.

The terpene of the component (c) used in the present invention includes monoterpenes, sesquiterpenes, diterpenes, terpene alcohols, terpene ketones and the like.
Specific examples of these are myrcene, ocimene, limonene, terpinolene, terpinene, sabinene, karen,
Monoterpenes such as pinene and camphene; curcumen,
Sesquiterpenes such as kadinene; diterpenes such as camphorene and millen; terpene alcohols such as citronellol, geraniol, nerol, linalool;
Mention is made of terpene ketones such as mentone, piperitenone and caron. These terpenes are used alone or in combination of two or more. Among these terpenes, limonene and terpinene are preferable, and limonene is particularly preferable, in terms of securing sufficient appearance restoring property. The compounding amount in the composition of the present invention is preferably 2 to 15% by weight.

The weight ratio (b) / (c) of the component (b) to the component (c) in the composition of the present invention is particularly important for ensuring low-temperature stability and appearance restorability. (B) /
The weight ratio of (c) needs to be 1/3 to 4/1, preferably 2/5 to 3/1. If it is less than 1/3, sufficient low-temperature stability and appearance restoring property cannot be ensured. If it exceeds 4/1, undesirable phenomena such as gelation appear in properties.

As the alcoholic organic solvent of the component (d) used in the present invention, ordinary alcohols can be used, and examples thereof include monohydric alcohols, dihydric alcohols, trihydric or higher alcohols, and alkoxy alcohols. Specific examples of these include ethanol, propanol, isopropanol, 3-methyl-3-methoxy-
Monohydric alcohols such as 1-butanol and benzyl alcohol; ethylene glycol, propylene glycol,
Dihydric alcohols such as 1,3-butanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol and tripropylene glycol; trivalent alcohols such as glycerin, sucrose, glucose, sorbitol and sorbitan There are the above alcohols, and examples of the alkoxy alcohol include ethyl cellosolve, propyl cellosolve, butyl cellosolve, ethyl carbitol, propyl carbitol, butyl carbitol, hydroxyethyl phenol, and ethylene glycol benzyl ether. These alcoholic organic solvents may be used singly or in combination of two or more, and the blending amount in the composition of the present invention is preferably 2 to 50% by weight.

The weight ratio of component (c) to component (d) and the sum of components (a) and (b) in the composition of the present invention {(c) + (d)} / {(a) + (B)} is particularly important for ensuring low-temperature stability and appearance restorability,
The numerical value needs to be 1/5 to 2/1, preferably 1/4 to 3/2. If it is less than 1/5, sufficient low-temperature stability and appearance resilience cannot be secured,
If it exceeds 2/1, a better effect cannot be expected even if it is further increased.

The detergent composition of the present invention is usually used after being diluted with water, but may contain other surfactants within a range not to impair the effects of the present invention. Examples thereof include amphoteric surfactants such as alkylamine oxides, fatty acid alkanolamides and polyoxyalkylene derivatives thereof, and amphoteric surfactants such as alkyl betaines, fatty acid amide propyl betaines, and imidazolium betaines. Also,
It can contain builders, optical brighteners, enzymes, anti-redeposition agents, chelating agents, bleaching agents, preservatives, dyes, fragrances, extracts and the like which are generally added to detergent components.

[0018]

EXAMPLES The present invention will be specifically described with reference to examples. EXAMPLES AND COMPARATIVE EXAMPLES The detergent compositions were prepared from the raw materials shown in Table 1 by using the formulations shown in Table 2, and tested for detergency, washing feeling, low-temperature stability and appearance restoring property. Was evaluated. The results are also shown in Table 2. The test methods and evaluation methods performed in the examples are shown below.

(1) Evaluation of detergency A detergency test was performed according to the following method. The composition of the artificially stained cloth used and the method for evaluating the cleaning power are as follows. (A) Detergency test 1 The following amount of the detergent composition was added to 500 ml of tap water, placed in a 1-liter beaker, and two 10 cm × 10 cm artificially stained cloths were immersed in the beaker and washed. The washing conditions are shown below. <Washing conditions> Soaking time 20 minutes Cleaning composition in Table 2 (a) Calculated amount when the amount of nonionic surfactant used becomes 0.25 g Soaking temperature 20 ° C Rinsing Shaking rinse Dehydration Dehydration tank rotation 10 seconds after stabilization

(B) Detergency test 2 A 30 × 30 cm cotton sewn with 2 kg of cotton towel and four 10 × 10 cm artificially stained cloths at a water level in a wool course of a washing machine (AW-65VF3 manufactured by Toshiba Corporation). I washed my gold cloth. The washing conditions are shown below. <Washing conditions> Water amount 63 liters Washing time 4 minutes Cleaning composition of Table 2 (a) Calculated amount to use 31.5 g of nonionic surfactant Washing temperature 20 ° C Rinse and rinse twice 2 Dehydration 40 seconds <Soil composition of artificially contaminated cloth (% by weight)> Oleic acid 15.0 Palmitic acid 7.5 Myristic acid 7.5 Tallow hardened oil 30.0 Cholesterol 10.0 Squalene 5.0 Cetyl alcohol 10.0 Paraffin 15. 0 A mixture of 60 parts by weight of this soil and 10.5 parts by weight of carbon black dispersed therein was designated as artificial stain, which was used to contaminate a white cloth (cotton gold cloth) to obtain an artificially stained cloth.

<Evaluation Method of Detergency> After drying the contaminated cloth, the surface reflectance was measured with a color computer (manufactured by Suga Test Instruments Co., Ltd.), the detergency was calculated from the following equation, and the average value was calculated as follows. The evaluation was made in two stages.

[0022]

(Equation 1)

The detergency was evaluated according to the following criteria. ：: Good detergency (35% or more) ×: Low detergency (less than 35%)

Evaluation method of texture after washing A texture test was performed according to the following method. (A) Preparation of Test Cloth The two stained cloths prepared in the cleaning power test 1 after washing were naturally dried and evaluated. (B) Evaluation of texture Ten women were panelists, and the feel of the test cloth was paired with the control cloth (white cloth washed with water) according to the following criteria. The scores of 10 persons were totaled, and those showing a total value of 26 points or more were evaluated as detergent compositions having good texture. 4 points: When feeling considerably softer than the control cloth 3 points: When feeling slightly softer than the control cloth 2 points: When feeling equal to the control cloth 1 point: When feeling slightly harder than the control cloth 0 Point: If you feel much harder than the control cloth

(3) Evaluation of Low-Temperature Stability of Composition 80 ml of the detergent composition was weighed into a 100-ml glass vial, stored at 5 ° C. for 24 hours, and the fluidity was visually determined according to the following criteria. . ：: When the fluidity of the composition was sufficiently recognized X: When the composition was solidified or gelled

(4) Evaluation of appearance restoring property of composition:
After storage at 0 ° C. for 24 hours, fluidity and transparency were visually determined according to the following criteria. ：: Fluid, uniform and transparent ×: Non-uniform such as white turbidity or sediment, or gel-like lump

[0027]

[Table 1]

[0028]

[Table 2]

From Examples 1 to 9, all of the liquid detergent compositions using the components of the present invention are excellent in detergency, washing feeling, low-temperature stability of the composition, and appearance restoring property of the composition. Was. In Comparative Examples 1 to 7, sufficient performance was not obtained. In Comparative Example 1, since the value of (a) / (b) was small, the cleaning power was poor. In Comparative Example 2, since the value of (a) / (b) was large, the texture after washing was inferior. In Comparative Example 3, since the value of (b) / (c) was small, the low-temperature stability of the composition and the appearance restoring property of the composition were poor. In Comparative Example 4, (b) /
Since the value of (c) is large, the low-temperature stability of the composition and the appearance restoring property of the composition are poor. In Comparative Example 5,
Since the value of {(c) + (d)} / {(a) + (b)} is small, the low-temperature stability of the composition and the appearance restoring property of the composition are poor. In Comparative Example 6, {(c) + (d)} /
Since the value of {(a) + (b)} is large, the appearance restoring property of the composition is poor. In Comparative Example 7, the component (c) was not contained, and the value of (b) / (c) was out of the range of the present invention. Therefore, the low-temperature stability of the composition and the appearance restoring property of the composition were poor. ing.

[0030]

The cleaning composition of the present invention is excellent in biodegradability, has excellent cleaning effect even with small mechanical force, and has a good finish after washing. The effect can be demonstrated. In addition to having good low-temperature stability and sufficient appearance restoring properties, it can be used in various climates.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C11D 3/18 C11D 3/18 3/43 3/43 17/08 17/08

Claims (1)

[Claims] 1. The composition contains the following components (a) to (d):
(A) / (b) weight ratio of 2/1 to 20/1, (b) /
The weight ratio of (c) is 1/3 to 4/1, and {(c) +
(D)} / {(a) + (b)} weight ratio is 1/5 to 2 /
1. A liquid detergent composition, which is 1. (A) Nonionic surfactant (b) Tertiary amine salt or quaternary ammonium salt type cation having an ester bond or an amide bond and having at least one acyl group having 12 to 22 carbon atoms in the molecule Surfactant (c) Terpene (d) Alcohol organic solvent