JPS62199697A - Liquid detergent composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a novel phosphorus-free liquid detergent composition. More specifically, it has high detergency and low foaming properties, making it especially suitable as a laundry detergent, as well as the iron content (-) that can prevent the yellowing of fibers that occurs. Novel liquid detergent composition of phosphorus type (= related to).

BACKGROUND OF THE INVENTION Generally, in the laundry industry, a tataki washing method using a drum-type washing machine, which is different from an agitation-type washing machine for general household use, is used as a washing method. In this cleaning method, the bath ratio is usually about 1:5 to 1:10 and the cleaning temperature is as high as 50 to 70°C, so ordinary detergents tend to cause foaming. Since this causes a decrease in cleaning effectiveness, laundry detergents are particularly required to have low foaming properties.

On the other hand, in laundry cleaning, automatic detergent injection systems have become popular in order to continuously process large quantities of laundry, and there is therefore an increasing demand for liquid detergents that can be easily transported through pipes.

Another characteristic of laundry washing is that, as seen in the linen supply industry, for example, sheets, wrappers, white coats, cook's clothes, tablecloths, towels, etc. are then collected and washed again and again. Unlike the laundry of
When white items to be washed turn yellow, their fresh image is significantly impaired, so they lose their value as a product and must be discarded. One of the major causes of yellowing of the items to be washed is that a small amount of iron contained in the water as insoluble colloidal iron adsorbs to the fibers and causes them to turn yellow. Therefore, laundry detergents are required to have low foaming properties and to prevent the yellowing of fibers caused by the iron contained in the laundry water.

On the other hand, as research on the effects of phosphates on the social environment progresses, phosphates, which have traditionally been used as builders in cleaning agents, have become a problem, and research has recently begun to develop phosphorus-free cleaning agents. It is being actively carried out.

Examples of phosphorus-free liquid cleaning compositions include LA
A mixture of S, AO8, AmS and a polymaleate (Japanese Unexamined Patent Publication No. 71408/1983),
Hard surface cleaning agent containing alkali hydroxide, 2-hydroxyethyliminodiacetate, and a copolymer of isoamylene and maleic anhydride (Japanese Patent Application Laid-open No. 198598/1983)
etc. have been proposed.

However, the former composition (=) has the problem that sufficient cleaning power cannot be expected unless it is combined with an alkaline agent, and it foams too much, making it unsuitable as a laundry detergent. This applies to cleaning equipment, etc., and is not intended for textiles.

In addition, other liquid cleaning compositions include surfactants, inorganic builders, benzenesulfonic acids, polyhydric carboxylic acids,
Contains alkanolamide and no organic solvent at all (Japanese Patent Application Laid-open No. 52-82908), LAS, fatty acid potassium soap, nonionic surfactant, maleic anhydride copolymer, and sodium tripolyphosphate. (Japanese Unexamined Patent Publication No. 51-133306) has been disclosed.

However, the former composition has the drawbacks of high foaming properties and insufficient yellowing prevention effects, while the latter compositions have low foaming properties and high detergency, but , there is a problem in that it is phosphorus-containing.

Problems to be Solved by the Invention As described above, the phosphorus-free type has excellent cleaning power comparable to phosphorus-containing types, has low foaming properties, has good stability, and is resistant to water. A liquid detergent composition suitable for laundry use that can prevent the yellowing of fibers caused by the iron contained in the laundry has not yet been found.

Under these circumstances, an object of the present invention is to provide a phosphorus-free liquid detergent composition having the above-mentioned properties, which is particularly suitable for laundry use.

Means for Solving the Problems As a result of extensive research, the present inventors have found that higher fatty acid soaps, detergent surfactants, alkaline chemicals, and copolymers of alkylene and maleic anhydride or their salts are combined in specific proportions. It has been discovered that a liquid detergent composition containing the following can meet the above-mentioned purpose, and based on this finding, the present invention has been completed.

That is, the present invention provides (A) higher fatty acid soap 0.5
~10% by weight, C) 3-20% by weight of detersive surfactant,
(C') Alkaline chemical 1-15 weight ratio and (D) 10-
Copolymer of alkylene having 5 to 8 carbon atoms and maleic anhydride having a degree of polymerization of 100, alkali metal salt, ammonium salt or alkanol-substituted ammonium #L0.
The present invention provides a liquid detergent composition containing 3 to 10% by weight and having a weight ratio of component (B)/(→component) in the range of 0.5 to 50.

The higher fatty acid soap used as component (A) in the composition of the present invention is a salt of a higher fatty acid and an alkali, and examples of this salt include monovalent alkali metal salts such as sodium and potassium, ammonium salts, or monoethanol salts. , jetanol, aminoethylethanol-substituted ammonium salts, among which potassium salts and monoethanol-substituted ammonium salts are preferred.

The higher fatty acids preferably have 8 to 22 carbon atoms, particularly 12 to 18 carbon atoms, and may also be saturated fatty acids,
It may be an unsaturated fatty acid or a mixed fatty acid. Specific examples of higher fatty acid soaps include potassium stearate soap, monoethanolamine oleate soap, potassium laurate soap, potassium tallow fatty acid soap, sodium soybean oil fatty acid soap, potassium coconut fatty acid soap, and the like.

One type of these higher fatty acid soaps may be used, or two types may be used.
They may be used in combination of two or more kinds, and the blending amount is selected within the range of 0.3 to 10% by weight, preferably 0.5 to 8% by weight based on the composition. If this amount is less than 0.3% by weight, foaming will not be sufficiently suppressed, and if it exceeds 10% by weight,
This is not preferable because a large amount of scum is generated in the washing liquid and the stability of the composition is deteriorated.

The detersive surfactant used as component (B) in the composition of the present invention is not particularly limited, but anionic or nonionic surfactants are generally preferred. Examples of anionic surfactants include alkylbenzene sulfonates, α-olefin sulfonates, alcohol sulfates, alcohol ethoxy sulfates, etc. In the form of salts, monovalent alkali metal salts such as sodium and potassium salts, ammonium salts, etc. , or monoethanol, jetanol, and aminoether ethanol-substituted ammonium salts, among which potassium salts and monoethanol-substituted ammonium salts are preferred. On the other hand, examples of the valve ionic surfactant include polyoxyethylene (n=10) nonylphenyl ether,
Examples include polyoxyethylene (n=15) dodenyl ether and polyoxyethylene (n=10) oleate ester. These nonionic surfactants usually have an average number of added moles n of polyoxyethylene groups of 3 to 3.
40, especially in the range 5 to 20 (- is preferred).

These detersive surfactants may be used alone or in combination of two or more, regardless of whether they are anionic or nonionic, and the blending amount is 3 to 20% by weight based on the composition. , preferably in the range of 5 to 15% by weight. When this amount is less than 3% by weight, sufficient detergency cannot be obtained, and when it exceeds 20% by weight, the stability of the composition tends to decrease and foaming properties tend to increase, which is not preferable.

In the composition of the present invention, (B
) It is necessary that the weight ratio (B)/(A) of the components be in the range of 0.5 to 50. If this ratio is less than 0.5, there will be more scum floating in the cleaning solution and the cleaning performance will decrease.
Moreover, if it exceeds 50, foaming cannot be sufficiently suppressed, which is not preferable. A suitable blending ratio is a weight ratio of component (B)/component (A) of 1 to 30.

In the composition of the present invention, the alkaline agent used as component (C) is a compound that exhibits strong alkalinity when made into an aqueous solution, and examples of inorganic alkaline agents include alkali metals such as potassium hydroxide and sodium hydroxide. hydroxide, carbonates and silicates such as sodium carbonate, potassium metasilicate, sodium orthosilicate, and sodium sesquisilicate, while organic alkaline agents include monoethanolamine, jetanolamine, amino Examples include amines such as etherethanolamine and triethanolamine.

Each of these alkaline chemicals may be used alone or in combination of two or more, and the blending amount is selected within the range of 1 to 15% by weight, preferably 2 to 10% by weight based on the composition. It will be done. If this amount is less than 1% by weight, the detergency will be insufficient, and if it exceeds 15% by weight, other components will be salted out, resulting in separation into two layers or gelation, which is unfavorable for the appearance of the product. Furthermore, the foamability also increases.

In the composition of the present invention, 1 used as component (D)
A copolymer of alkylene having 5 to 8 carbon atoms and maleic anhydride having a degree of polymerization of 0 to 100, an alkali metal salt thereof,
The ammonium salt or alkanol-substituted ammonium salt has the general formula (-e R2+ R1 and R4 are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and '!+ "x lR
The total number of carbon atoms in 3lR4 is 5 to 6, M is a hydrogen atom,
It has a structure represented by an alkali metal or unsubstituted or alkanol-substituted ammonium group, where X is about 0.6 and n is a number in the range of 10 to 100.

As the salt of the copolymer, alkali metal salts such as sodium, potassium, and lithium salts, ammonium salts, mono-, di-, and triethanol-substituted ammonium salts, aminoethyl ethanol-substituted ammonium salts, and the like are used.

In addition, those in which the alkylene unit in the copolymer has less than 7 carbon atoms have poor yellowing prevention effect and detergency;
If it exceeds the above range, the solubility of the copolymer becomes low, the anti-yellowing effect and detergency are reduced, and it is also unfavorable from the viewpoint of product appearance.

Furthermore, the copolymer has a degree of polymerization in the range of 10 to 100, preferably 20 to 80. If the degree of polymerization is less than 10, the anti-yellowing effect is significantly inferior;
Moreover, the detergency is also low; on the other hand, if it exceeds 100, the viscosity increases significantly and the product becomes gelled, which is unfavorable in terms of product appearance, and furthermore, the anti-yellowing effect and detergency tend to decrease.

The copolymer usually contains about 60 mol of maleic acid units.

These copolymers or salts thereof may be used alone or in combination of two or more.

In the composition of the present invention, the copolymer is added to the composition,
It is necessary to mix in the range of 0.3 to 10% by weight. If this amount is less than 0.3% by weight, the anti-yellowing effect and detergency will be poor, and if it exceeds 10% by weight, the stability of the composition will decrease.

In the composition of the present invention, the composition is usually added to a liquid cleaning composition for the purpose of increasing the solubility of cleaning ingredients in water in the composition, improving fluidity, and improving product stability. Hydrotropes can be added as desired. Examples of the hydrotrope include methanol, ethanol, inglobil alcohol, ethylene glycol, furopylene gellicol, liquid polyethylene glycol, sodium benzenesulfonate, sodium p-toluenesulfonate, and urea. These hydrotropes are usually incorporated in the composition in an amount ranging from a few centimeters to at most 15% by weight. Even if a large amount of this substance is blended, the product stability does not improve in proportion to the amount; rather, it is greatly influenced by the quality and quantity of other imaginary components in the composition.
・1 Furthermore, the composition of the present invention (2) can also contain a chemical compound as desired. Conventionally, most detergents for textile products have contained a chemical compound, but recently, The safety of party rules is being debated,
In the laundry industry as well, there is a tendency not to use detergents containing Kyoto's Law in detergents for textile products that come in direct contact with food and drink, but there is a tendency to use detergents containing Kyoto's Law for items to be washed such as clothing and bedding. It is commonly used, and there is no problem in adding it to the composition of the present invention. When the composition of the present invention is blended with the sinter rule, the quenching effect of the sinter rule due to iron adhesion can be inhibited, so that the orienting effect of the sinter rule can be effectively exhibited.

Effects of the Invention Although the liquid cleaning composition of the present invention is a phosphorus-free type, it has excellent cleaning power comparable to a phosphorus-containing type, has low foaming properties, and has good stability. Furthermore, it has excellent characteristics such as being able to prevent the yellowing of fibers caused by iron contained in water, and is particularly suitable for use as a laundry detergent.

EXAMPLES Next, the present invention will be explained in more detail with reference to examples. In addition, each performance was evaluated as follows.

(1) Evaluation of cleaning power (1) Preparation of artificially soiled cloth Clay containing crystalline minerals such as kaolinite and vermiculite as the main components was heated at 200°C and 130°C as inorganic soil.
After drying for an hour, it was ground to an average particle size of 1 μm and used. Gelatin 3.51 in 950 cc of water at about 40°C
After dissolving in the Polytron (
Made in Switzerland by NEMAT CA) 0.25. iil of carbon black was dispersed in water. Next, inorganic dirt 1
Add 4,911 and disperse with Polytron, and then organic dirt 31,351! Add poly1. It was emulsified and dispersed to create a stable dirt bath. In this dirt bath (=10cI
IX203 specified cleaning cloth (Japan Oil Chemists Association designated cotton cloth 6
0), squeeze out the water with two rubber rolls,
The amount of dirt attached has been made uniform. After drying this soiled cloth at 105° C. for 30 minutes, both sides of the soiled cloth were rubbed 25 times on each side. This was cut into 5aR x 5C11K pieces with a reflectance in the range of 42±2% and used as a dirty cloth. The soil composition of the artificially soiled cloth thus obtained is shown in Table 1.

Table 1 (II) Prepared Sebum cloth (cotton knitted 5 ctx x 5 tyx) with organic dirt 601n9 shown in Table 1 attached to each fabric.

(2) Clean knitted cloth Cotton stockinette (same material used for sebum cloth).

■ Cleaning method The cleaning device is Terg-0- manufactured by G, B, and Testing.
Using a T
Do this for minutes. The water used was 50 DH.

M Detergency Evaluation Method R is the reflectance @) measured by a Carl Zeiss IREPHo reflectance meter. The detergency was evaluated using the average value of 10 artificially soiled cloth samples.

(2) Rothsmiles method (JK S K3362) using a detergent aqueous solution with a foaming detergent concentration of 0.167%, hardness of 3aDH, and liquid temperature of 60°C
After dropping into a receiver, measure the foam height 1 minute later.

(3) Evaluation of anti-yellowing power (1) Preparation of iron dispersion Dissolve ferric chloride (special grade reagent) in pure water so that the iron concentration is 2 ppm (= - of this aqueous solution is about 2 to 3 A potassium hydroxide aqueous solution is added dropwise to this solution while stirring and adjusted to approximately PI (7). At pH 7, iron is in a dispersed state as water-insoluble fine particles.

(It) Test fabric Non-fluorescent fabric (cotton broadcloth #: 40) 5x5 (71I
Size (III) Treatment method U, S, Testing Terg-0-Tomet
Iron dispersion 900 adjusted to hardness 3°DH using er
．． 7 and raise the temperature to 60°C. Put the test cloth sag,
After adding an amount equivalent to 0.167% concentration of cleaning agent, 120 rpm
m for 10 minutes. After that, the weight of the test cloth is about 90
Add 900 txl of fresh 30DH iron dispersion to the dehydrated product and rinse at 40°C for 6 minutes at 12 rpm.This rinsing operation is performed twice.The washing and rinsing steps are completed in one time. Wash cycle and repeat a total of 3 times.

(■) After drying the test cloth after yellowing measurement treatment, use a color difference meter (Σ80color
The yellowness value was measured using a measuring system (Nippon Heavy Industries KK), and the yellowness degree was expressed as the Δb value.
0...' before treatment (4) Product stability Place the product in a transparent plastic container at 100%. / and stored in a sealed state in a constant temperature room set at each temperature (-5°C to 45°C), and the appearance of the product was evaluated after 24 hours.

Judgment criteria: ○: Uniform, transparent liquid with good fluidity △: Slight sedimentation or separation, but at room temperature (
After two apparatuses, it becomes a homogeneous transparent liquid.

x: The whole is cloudy, separated, or gelled, and has no fluidity.

(5) Appearance of cleaning solution The appearance of an aqueous cleaning solution with a cleaning agent concentration of 0.167 mm, hardness of 30 DH, and liquid temperature of 60° C. was visually evaluated.

○...Scum is not floating on the surface of the cleaning agent aqueous solution.

×... Scum floats on the surface of the cleaning agent aqueous solution and forms a film.

Example A liquid cleaning composition having the composition shown in Table 2 was prepared,
The performance was evaluated and the results are shown in Table 2.

Claims (1)

[Claims] 1 (A) 0.3 to 10% by weight of higher fatty acid, (
B) 3-20% by weight of a detersive surfactant, (C) 1-15% by weight of an alkali agent, and (D) a copolymer of a C5-8 alkylene with a degree of polymerization of 10-100 and maleic anhydride. containing 0.3 to 10% by weight of at least one selected from the group consisting of alkali metal salts thereof, ammonium salts, and alkanol-substituted ammonium salts, and has a component (B)/component (A) weight ratio of 0.5. 50.