JPS5837356B2 - Ekita Senjiyouzai Sobutsu - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a liquid detergent composition with good low-temperature stability, which has a low content of phosphorus compounds or substantially does not contain them, in particular, has little change in viscosity due to temperature, has little skin irritation, and has cleaning power. ,
This invention relates to a well-balanced liquid cleaning composition with good foaming and rinsing properties.

Conventional liquid detergents are inconvenient to handle at low temperatures due to the strong temperature dependence of their viscosity, and phenomena such as precipitation, clouding, and solidification due to decreased solubility in water at low temperatures. Problems such as the difficulty in restoring a partially solidified material to a homogeneous liquid state even when heated and melted can be solved to a certain extent by using quite large amounts of so-called hydrotropes such as lower alcohols, lower alkanolamines, lower alkylbenzenesulfonates, and urea. solving the problem.

However, hydrotropes contribute little to the cleaning action, limit the content of cleaning ingredients in liquid cleaning compositions, increase costs, and reduce B. 0. D. YaC
．． 0. D. or cause new problems such as increased skin irritation.

Further, the odor peculiar to hydrotropes and the odor of their decomposition products are also undesirable.

Furthermore, since a hydrotrope is used, a viscosity improver at room temperature and a decomposition inhibitor for urea and the like are added, which is a drawback.

Furthermore, conventional liquid detergents contain phosphoric acid builders such as pyrophosphates in order to obtain detergency.

However, it is said that phosphorus compounds enter the water and cause eutrophication of microorganisms, so it is not preferable to use them.

The present invention provides a well-balanced liquid detergent combination with excellent performance, which eliminates the need for hydrotropes and phosphoric builders, and solves the problems of the prior art.

That is, the composition of the present invention has the following formula: a) General formula R'O (C2H40)nH (wherein R1:
C7 to C12 straight or branched alkyl group, n: average number of 4 to 12) Intermediate alcohol ethoxylate 5 to 50wt
% and b) a sulfuric acid ester type anionic compound represented by the general formula R20(C2H40)mSOsH (where R2: C12 to C15 linear or branched alkyl group, m: average number of O to 5) Contains 5 to 50 wt% of an alkali metal salt, ammonium salt or alkanolamine salt of a surfactant, and further contains as an impurity: C) General formula R30H (wherein R3: C7 to C1, linear or branched alkyl group) C7-Cl alcohol 0.1 wt% or less based on the sum of components a) and b), CI
2~C13 alcohol 2.0wt% or less and C14~
C,5 alcohol within the range of 1.5 wt% or less, and C7
- Contains 2.5 wt% or less in total amount of C15 alcohol, and the sum of components a) and b) is 30 to 65 wt%
It is characterized in that the ratio of a) precepts to b) precepts is in the range of 4/1 to 1/4.

Component a), that is, intermediate alcohol ethoxylate, is prepared by adding ethylene oxide (EO) to an alcohol having the above carbon number using an alkali catalyst (NaOH, KOH, CHs, ONa, C
H3, OK, amine, etc.) or acid catalysts (SnC4, S
bCA',, BF3, OR2, etc.) at low temperature (approximately 4
It can be obtained by adding EO at temperatures ranging from 0°C to high temperatures (approximately 200°C), but even if a tilted type catalyst is used, EO cannot be obtained.
Even if the average number of moles added is in the range of 4 to 12, the distribution of the number of moles added is wide ranging from 0 moles to 20 moles or more.

The problem varies depending on the catalyst, but is there a relatively large amount of unreacted alcohol? It is to remain.

For example, commercially available intermediate alcohol (product name Diadol 11)
) 49.6 parts by weight was added to S ncl4 o. When 50.4 parts by weight of EO is reacted at 45°C for 13 hours in the presence of 25 parts by weight, alcohol ethoxylate with an average added mole number of 4.0 is obtained, and unreacted alcohol is about 0% of the product.
．． It is present at 5wt%.

On the other hand, when NaOH is used as a catalyst and the reaction is carried out at 180° C. for 2 hours, about 10 wt % of unreacted alcohol remains in the alcohol ethoxylate with an average added mole number of 4.0.

The present inventors have discovered that such unreacted alcohol deteriorates the physical properties of the liquid cleaning agent.

That is, intermediate alcohols increase the temperature dependence of viscosity, and tend to precipitate from liquid detergents at low temperatures, contributing to cloudiness or solidification.

Furthermore, it has the disadvantage of increasing skin irritation.

Therefore, the alcohol ethoxylate used in the present invention is substantially free of unreacted alcohol.

When this intermediate alcohol ethoxylate is used in combination with an anionic surfactant, as the number of carbon atoms increases, foaming decreases and rinsability also deteriorates.

Therefore, the number of carbon atoms in the alkyl group must be substantially free of CI3 or more, and CI2 must be 30 wt% or less.

Further, since the detergency of C8 or less is low, it is preferably 25 wt% or less.

The composition of the present invention uses 5 to 50 wt% of alcohol ethoxylate having such carbon distribution, but this nonionic surfactant alone does not have sufficient cleaning power and foaming power is quite low. When used in combination with an anionic activator, complementary superior detergency and foaming power can be obtained.

Such anionic surfactants are used as component b).

When used alone, this anionic activator has poor cleaning power similar to intermediate alcohol ethoxylates, but sufficient performance can be obtained by using it in combination with the alcohol ethoxylate of component a).

Those with a small number of carbon atoms in the alkyl group have low foaming and do not have sufficient cleaning power.

As the number of carbon atoms increases, the cleaning power and foaming power improve, but the rinsability, cold resistance, solution viscosity, etc. gradually deteriorate, making it unsuitable.

Therefore, the carbon number is preferably C1 to C15, and anything outside this range is not preferred.

Alkali metal salts are preferably sodium salts or potassium salts, and alkanolamine salts are preferably ethanolamine salts. Propanolamine salts, preferably ethanolamine salts.

The appropriate amount used is 5 to 50 wt%.

In the detergent composition of the present invention, the surfactants that provide detergent activity are mainly components a) and b), and the sum of these is contained in a relatively high concentration of 30 to 65 wt%, and a)
It is important that the ratio of component to component b) is 4/1 to 1/4.

Conventional liquid detergents use relatively large amounts of solubilizers and the like to balance various performances, so it has not been easy to obtain products containing a high concentration of surfactants.

In the present invention, components a) and b) are used in a specific ratio, so that the unreacted alcohol contained in the a) component is substantially not contained, and the unreacted alcohol contained in the b) component is reduced to a certain level. By this, and more preferably by keeping the water-soluble inorganic salt to 2% by weight or less, the surfactant can be contained at a relatively high concentration, and the detergency, foaming, low-temperature stability, and stability of viscosity change against temperature changes can be improved. , hypoallergenic,
A liquid detergent composition that satisfies many performance requirements such as improved rinsability in a well-balanced manner can be obtained.

C) A part of the present invention defines the permissible limit of unreacted alcohol that inevitably remains when producing a) A part and b) Unreacted alcohol derived from the component a) This means that the amount of unreacted alcohol derived from component b) is kept to a minimum.

In other words, since C7 to C11 intermediate alcohols are irritating to the skin and have a large viscosity change with temperature, 0.1 wt.
% or less.

In addition, some of the C1 to C13 intermediate alcohols are a)
It comes from the ingredients, and most of it comes from the precepts (b), but it worsens cold resistance and increases viscosity change, so it needs to be kept at 2.0 wt% or less.

Furthermore, C14-C15 intermediate alcohol is C1-C13
Since it has a greater influence on cold resistance and viscosity change than alcohol, it must be kept at 1.5 wt% or less.

Moreover, the total amount of unreacted alcohols from C7 to CI5 is 2.
Only when the content is 5 wt% or less, a liquid detergent that is less irritating to the skin, has good cold resistance, and has a stable viscosity against temperature changes can be obtained.

The liquid detergent composition of the present invention preferably contains a C1 to C3 lower alcohol in a range of 7 wt% or less. In addition to being used as a drotrope, other hydrotropes, organic builders, fluorescent agents, colorants, fragrances,
Various additives such as antioxidants can be used.

The total amount of such additives used is suitably 15 wt% or less.

The composition of the present invention obtained in this way not only satisfies the essential performance as a cleaning agent in a well-balanced manner, such as cleaning power, foaming during cleaning, rinsability, and safety, but also has low-temperature stability. (cold resistance), viscosity stability against temperature changes, and skin irritation, and also has good biodegradability, does not cause eutrophication problems, and improves the texture of washed items. It has excellent performance or effects, such as not imparting a foreign odor to the items to be washed, being easy to handle, and convenient for transportation.

EXAMPLES The present invention will be explained in more detail with reference to Examples below.

Example 1 A liquid cleaning agent with the following composition was prepared and its performance was evaluated.

Oxo method for C9 to C11 (average C9.3) Average 8.0 mole adduct of ethylene oxide (EO) to alcohol listed in Table 1 (intermediate alcohol ethoxylate) Oxo method for CI2 to C13 (average, .4) Alcohol sulfate ester triethanolamine salt listed in Table 1 (anionic surfactant) Ethanol 6wt% Triethanolamine 1 Monoethanolamine 2 Fluorescent agent 1 Sodium benzoate 0.3 Fragrance
0.2 water
The remaining results are shown in Table-1.

Example 2 A liquid cleaning agent with the following composition was prepared and its performance was evaluated.

Intermediate alcohol ethoxylate 1.25 wt% anionic surfactant 25 (triethanolamine salt) Ethanol 6 Triethanolamine 1 Seven ethanolamine fluorescent agent Sodium benzoate wt% 0.3 Fragrance water Table 2 Results Shown below.

0.2wt% Residual Test Method■) Apply a sample of detergent gold cloth to the collar of clothing such as work clothes or dress shirts,
After being worn for 2 to 7 hours and becoming contaminated, they are removed and cut in the middle to prepare 20 pieces each.

Separately, a cotton knitted cloth shirt was worn for two days, divided symmetrically, and one side of each contaminated cloth was washed with standard cleaning agents (18% sodium linear alkylbenzene sulfonate, 25% sodium tripolyphosphate, 5% sodium silicate, carbonic acid). Soda 3%, CMCI
%, Glauber's Salt 43%, Water 5%), one of which was used as an exemplary cleaning agent, and washed and rinsed using a jet electric washing machine.

Cleaning agent concentration 0.14%, liquid volume 30L, hardness 3°DH
, temperature 25°C for 1 hour and 10 minutes.

Rinse with detergent-free water for 3 minutes under the same conditions as above.
Let's go around.

The cleaning power was determined by visually evaluating each pair of collar cloths on the left and right sides, and rated on a 5-point scale with a score of 5 for a pair of collar cloths that had almost completely removed the sewage, and a score of 1 for a pair of collar cloths that had almost no dirt removed. did.

The ratings are evaluated and expressed as an index with the standard detergent set at 100.

2) Foaming during cleaning After 5 minutes of cleaning, stop stirring temporarily, measure the foam height at several locations, and average.

3) Rinseability After rinsing twice, the case where the bubbles are completely gone is evaluated as A, the case where some bubbles remain is B, and the case where a lot of bubbles remain is C.

4) Viscosity ratio The viscosity is measured one hour after the specified temperature is reached using a BL type viscometer manufactured by Tokyo Keiki ■, and is calculated from the formula of viscosity ratio of 5°C.

Viscosity ratio A1 indicates that the viscosity at 25° C. is 10 or less, B1 indicates 11 to 20, and C indicates 21 or more.

5) Store the sample filled in a cold-resistant bottle at a low temperature for one day at 25°C.

This is regarded as one cycle, and after storage for 10 cycles, visually inspect the product. A uniform and transparent product is A1. A slightly cloudy product is B.
1 Precipitation, precipitation or solidification is evaluated as C.

6) Ten adults were immersed in a solution containing a skin-irritating detergent at a concentration of 2%, with both of their hands tied under the rain, immersed for 1 minute and dried with warm air for 1 minute, alternately 30 times, and observed for rough skin for 3 days. did.

The detergent temperature was 35°C.

The results are shown in Table 3. The erythema, papules, and desquamation shown in the disease symptoms in Table 3 indicate the following phenomena.

○ Erythema Appears as a fresh red color due to dilation and hyperemia of blood vessels or capillaries, and the red color fades when pressed with a glass plate.

0 points: No abnormality at all 2 points: patchy or mild 4 points: Flushing over almost the entire surface or something remarkable O Papula It is a cone-shaped rash that rises from the skin and varies in size.

The contents of the papules may be hard, similar to a stomatitis, or may have a feel similar to that of a water blister or small water droplet.

0 points: No abnormality at all 2 points: Scattered 4 points: Seed-like 0 Scale: The upper layer of the stratum corneum peels off as keratin flakes, which are extremely thin and fine bran-like and tree leaves. There are thick and large ones like .

O score: No abnormality at all 2 points: Partial or mild 4 points: Almost all over or noticeable The scores of the above 3 items were totaled for 10 people, and the score was 0 to 5.
．． 6-10 points are B1 11-15 points are C and 16
Scores of points or higher were rated D.

Claims (1)

[Claims] 1 a) General formula R' 0 (C 2 H, a O ) n H (wherein R1: C7 to C1 straight or branched alkyl group, n:
5 to 50 wt of intermediate alcohol ethoxylate (average number 4 to 12)
% and b) of the sulfate ester type anionic surfactant represented by the general formula R20(C2H40)mSO3H (where R2: C1 to C15 linear or branched alkyl group, m: average number of O to 5). C) an intermediate compound represented by the general formula R30H (wherein R3: C7 to C15 linear or branched alkyl group) containing 5 to 50 wt% of an alkali metal salt, ammonium salt, or alkanolamine salt; Alcohol is C7 to C1, 0.1 wt% or less, C,2 to C1s based on the sum of a) precepts and b) components
2. Owt% or less, C1, to C,5 1. 5 wt%
The total amount of C7 to C]5 intermediate alcohol is 2.5% or less in the following range, and the sum of a) component and b) component is 30 to 65 wt%, and a) component and b) component A liquid cleaning composition characterized in that the ratio of