JPH05171199A - Granular detergent composition having high bulk density - Google Patents

Abstract

PURPOSE:To obtain the subject composition, containing a specific sulfonate, an anionic surfactant, a silicate and a carbonate in a specified proportion, having a prescribed value or above of bulk density and excellent in detergency and preservation stability for a long period without causing sticking to cloths and useful for clothes, etc. CONSTITUTION:The objective composition containing (A) 1-5wt.% lower alkyl ester sulfonate of an 8-22C fatty acid, (B) 15-60wt.% anionic surfactant such as an alkanesulfonic acid other than the component (A), (C) 1-5wt.% silicate such as sodium silicate and (D) 10-40wt.% carbonate such as sodium carbonate. The bulk density of this composition is >=0.5g/cc.

Description

Detailed Description of the Invention

[0001]

The present invention has high cleaning performance,
The present invention relates to a high bulk density granular detergent composition which does not cause cloth adhesion.

[0002]

2. Description of the Related Art Conventional laundry detergents contain a bulking agent having a bulk density of 0.1% by adding an extender (usually Glauber's salt is used) that hardly contributes to the cleaning performance to the composition and spray drying the same.
It was manufactured as a bead-shaped hollow particle of about 3 g / cc.

However, since such a detergent has a low specific gravity and a low concentration of an activator, it is costly to transport and requires a considerable space for storage and display. Further, it is difficult to place it in a general household. It was difficult to weigh. Therefore, recently, a method for producing a high bulk density granular detergent which can be washed with a small amount of detergent has been proposed (JP-A-60-9).
No. 6698) has already been put on the market and has become the mainstream of granular detergents. Further, at present, there is a demand for the development of a high-bulk density detergent having a superior detergent performance as the basic performance of the detergent.

On the other hand, sulfonic acid salts of fatty acid lower alkyl esters are surfactants having excellent detergency, especially hard water resistance, and high bulk density detergent compositions containing them have been reported (for example, special (Kaisho 62-597). However, this uses only the fatty acid lower alkyl ester sulfonate as the main surfactant, and occupies more than half of the anionic surfactant blended in the detergent. In addition, the compounding amount of the fatty acid lower alkyl ester sulfonate is relatively large, and an example of about 10% or more is disclosed.

[0005]

DISCLOSURE OF THE INVENTION The present inventors mainly use anionic surfactants such as linear alkylbenzene sulfonates, α-olefin sulfonates, and alkyl sulphates which have been widely used for granular detergents. It was found that by using a fatty acid lower alkyl ester sulfonate as a small amount added activator, that is, as a so-called Co-Surfactant, the detergency is dramatically improved.

However, the fatty acid lower alkyl ester sulfonate has a problem that it is hydrolyzed with time and the ester bond is cleaved to change to a di-salt of a fatty acid sulfonate. Since this di-salt is inferior to the ester sulfonate in detergency, the initial detergency cannot be maintained. Especially as a co-surfactant,
When incorporated into a detergent composition containing a large amount of a liquid crystal-forming surfactant such as a linear alkylbenzene sulfonate or an α-olefin sulfonate, the degree of hydrolysis is large.

Further, there is a problem that the addition of the fatty acid lower alkyl ester sulfonate lowers the solubility and causes the cloth to adhere. The present invention provides a high bulk density granular detergent composition which uses a fatty acid lower alkyl ester sulfonate as a cosurfactant, has a high detergency even in long-term storage, and has good cloth adhesion.

[0008]

The fatty acid lower ester sulfonate used as a co-surfactant in the present invention exhibits a high detergency enhancing effect by addition, but on the other hand, it causes an increase in cloth adhesion. Therefore,
Improves cloth adhesion by adding silicate,
Furthermore, the physical properties of the powder are also improved. However, the addition of silicate causes hydrolysis of the fatty acid lower alkyl ester sulfonate over time. Therefore, in order to solve this problem, a predetermined amount of carbonate was added.

That is, the high-bulk-density granular detergent composition of the present invention is characterized by containing the following components (A) to (D) and having a bulk density of 0.5 g / cc or more. (A) Sulfonate of fatty acid lower alkyl ester having 8 to 22 carbon atoms in fatty acid residue: 1 to 5% by weight. (B) Anionic surfactant other than the component (A): 1
5 to 60% by weight, (C) Silicate: 1 to 5% by weight. (D) Carbonate: 10-40% by weight.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The sulfonic acid salt of a fatty acid lower alkyl ester as the component (A) is typically represented by the following chemical formula 1, which is also called an α-sulfo fatty acid ester salt.

[0011]

[Chemical 1] (R ^1: alkyl or alkenyl group R ^2: C ₁ ~C ₃ about a lower alkyl group M: counter ion)

As the counter ion, a water-soluble salt is used, but an alkali metal salt, especially a sodium salt is preferable.

The sulfonate of a saturated fatty acid lower alkyl ester is produced by transesterification or esterification of a fatty acid to produce a fatty acid lower alkyl ester having a predetermined number of carbon atoms, and then sulfonated with sulfuric acid anhydride or the like using an ordinary sulfonation apparatus. It can be obtained by reacting with an agent, aging if necessary, bleaching, and then neutralizing. It can also be obtained by converting a sulfonated fatty acid into a lower alkyl ester. Further, a sulfonate of an unsaturated fatty acid lower alkyl ester is also used, and is produced in the same manner as described above using an unsaturated fatty acid having a predetermined carbon number as a starting material.

As the raw material fatty acid, a fatty acid derived from beef tallow, coconut oil, palm oil or the like having a predetermined carbon number of animal or plant origin, or a synthetic fatty acid is used. The fatty acid residue (R ¹ —CHCO) of the fatty acid lower alkyl ester sulfonate has 8 to 22 carbon atoms, preferably 10 to 18 carbon atoms.

Examples of the anionic surfactant as the component (B) include the following. 1) Linear alkylbenzene sulfonate having an alkyl group having an average carbon number of 8 to 16; 2) α-olefin sulfonate having an average carbon number of 10 to 20; 3) Alkyl sulfate having an average carbon number of 10 to 20; ) A saturated or unsaturated fatty acid salt having an average carbon number of 10 to 22.

It is also possible to use other anionic surfactants such as alkane sulfonic acid and polyoxyethylene alkyl ether sulfate ester salt. Alkali metal salts such as sodium and potassium are usually suitable as counterions in these anionic surfactants.

The component (A) is used in the detergent composition in an amount of 1 to 5% by weight, and the component (B) is used in the form of a mixture of one or more components in the detergent composition in an amount of 15 to 60% by weight, preferably 2%.
0-40% by weight is compounded.

In the present composition, the component (B) is used as a main activator for cleaning. If the component (B) is less than 15% by weight, sufficient detergency cannot be obtained, while it exceeds 60% by weight. If the amount of the surfactant is too large, it will be difficult to manufacture by a usual manufacturing method.

The content of the component (A) is 1 to 5% by weight. Even if it is added in an amount of more than 5% by weight, the effect of improving the detergency is slight, while if it is less than 1% by weight, the effect of addition as a cosurfactant becomes small. Further, the mixing ratio of the component (A) and the component (B) is (A) / (B) =
5/95 to 25/75 are preferable, and 10 is more preferable.
/ 90 to 20/80. When the compounding ratio is 5/95 or less, a sufficient synergistic effect cannot always be expected, and the ratio of 25 /
If it is 75 or more, the effect may be saturated.

As the silicate which is the component (C),

Embedded image Sodium silicate represented by Na ₂ O.nSiO ₂ (n = 2.0 to 3.2) is preferable. Sodium silicate forms a strong network structure when dried,
It has the functions of improving the fluidity of powder and preventing metal corrosion, and is a very preferable base material as a builder for detergents. However, such silicates are non-crystalline, and the alkaline portion represented by Na ₂ O is S even when dried.
It cannot form crystals with the acidic portion represented by iO ₂ , and is considered to have a considerable amount of free water. Therefore, (A)
The fatty acid lower alkyl ester sulfonate, which is a component, is susceptible to hydrolysis. Furthermore, when a silicate coexists with an anionic surfactant that easily forms a liquid crystal such as the alkyl benzene sulfonate as the component (B), the hydrolysis of the sulfonate of the fatty acid lower alkyl ester by the silicate tends to be accelerated. is there.

In the detergent composition of the present invention, it is essential that the content of silicate is 1 to 5% by weight, preferably 2 to 4% by weight. If the content of silicate exceeds 5% by weight,
Upon storage, hydrolysis of the sulfonate of the fatty acid lower alkyl ester proceeds, and the initial detergency cannot be maintained.
On the other hand, if it is less than 1% by weight, the fluidity of the detergent particles and the cloth adhesion are poor, which is not preferable.

As the carbonate as the component (D), sodium carbonate, potassium carbonate and the like are used. Carbonate is blended in the detergent composition of the present invention in an amount of 10 to 40% by weight, preferably 15 to 30% by weight. The amount of carbonate is 1
If it is less than 0% by weight, the hydrolysis of the fatty acid lower alkyl ester sulfonate cannot be prevented, and the detergency is lowered. On the other hand, even if the carbonate is blended in an amount of more than 40% by weight, the effect of addition is already saturated and only the blending of other components is restricted.

Further, as the carbonate of the component (D),
It is preferable to mix (D ₁ ) sodium carbonate and (D ₂ ) potassium carbonate in a weight ratio of D ₁ / D ₂ = 80/20 to 25/75, whereby a fatty acid lower alkyl ester sulfonate is added. With the further effect of suppressing hydrolysis,
Good solubility of high bulk density granular detergents is obtained.

Furthermore, in addition to the above essential components, the high bulk density granular detergent composition of the present invention contains a surfactant, an inorganic salt, a chelate builder, an anti-soil redeposition agent, an enzyme, and a fluorescent agent which are usually added to detergents. Well-known ingredients such as fragrance, bleach, bleach activator and the like can be added.

Examples of the surfactant include nonionic surfactants such as alkyl and alkenyl ethers of polyoxyethylene, fatty acid esters, sugar fatty acid esters, alkylamine oxides, and cationic surfactants such as tetraalkylammonium chloride. There are amphoteric activators such as alkyl sulfobetaines and fatty acid sodium salts, so-called soaps, can be incorporated as foam control agents.

The chelate builder includes phosphates, polyacrylates, polycarboxylic acids, zeolites, etc., the anti-redeposition agent includes polyvinyl alcohol, carboxymethyl cellulose, etc., and the enzymes include protease, cellulase, amylase. , Alkaline lipase, etc.

Further, sodium percarbonate and sodium perborate as bleaching agents, TAED (tetraacetylethylenediamine), PAG (pentaacetylglucose) and TMP-Cl (1-chloro-4-hydroxy-2,2,2) as bleaching activators. 6,6-tetramethylpiperidine),
NOBS (nonanoyloxybenzene sulfonic acid) etc. can be used.

[0028]

According to the present invention, by using a fatty acid lower alkyl ester salt as a co-surfactant, it has a high detergency and is prevented from adhering to a cloth.
Hydrolysis of the fatty acid lower alkyl ester sulfonate is prevented even after long-term storage, and a high bulk density granular detergent composition exhibiting original cleaning performance can be obtained. The present invention is particularly useful when an anionic surfactant is incorporated as a main detergent for cleaning.

[0029]

Example A detergent slurry having a solid content of 45% was prepared by using the components shown in Table 2 below except for the nonionic surfactant. This detergent slurry was dried at a hot air temperature of 380 ° C. to a water content of 5% using a countercurrent spray drying tower to obtain a spray-dried product.

This spray-dried product has an average particle size of 350 μm,
The bulk density was 0.35 g / cc and the angle of repose was 45 degrees, and the fluidity was also good. Then, the dried product, nonionic surfactant and water were continuously kneaded (KRC Kneader # 2 manufactured by Kurimoto Iron Works Co., Ltd.).
It was introduced into a mold and a dense and uniform kneaded product was obtained.

At the outlet of this kneader, a hole diameter of 5 mmφ is 8
A perforated plate (thickness 10 mm) having 0 pieces was installed, and the kneaded product was made into a cylindrical pellet of about 5 mmφ × 10 mm. Crushing machine (speed mill ND-10 type, Okada Seiko Co., Ltd.) with a double amount (weight ratio) of cooling air at 15 ° C for this pellet
Introduced to. At this time, at the same time, 4 parts by weight of finely ground sodium carbonate as a grinding aid was added to 100 parts by weight of the pellets.

The crusher has a cutter having a length of 10 cm in four stages of cross, rotates at 3000 rpm, and the screen is made of 360-degree punching metal. This crusher is continuously connected in 3 stages, and the hole diameter of each stage screen is 1st stage; 3.5mmφ, 2nd stage; 2mmφ, 3rd stage; 1.5
mmφ. The particles that have passed through the crusher in three stages are separated from the cooling air, have the composition shown in Table 2 below, and have an average particle size of 50.
A high bulk density granular detergent composition having 0 μm and a bulk density of 0.8 g / cc was obtained.

With respect to each of these detergent compositions, the detergency and cloth adhesion, and the hydrolysis rate of the fatty acid lower alkyl ester sulfonate after storage were measured and evaluated, and the results are shown in Table 2.

(1) Method of evaluating detergency (I) Preparation of artificial dirt Clay containing crystalline minerals such as kaolinite and vermiculite dried at 200 ° C. for 30 hours is used as inorganic dirt. did.

About 3.5 g of gelatin in about 950 cc of water
After being dissolved at 0 ° C., 0.25 g of carbon black was dispersed in water with a powerful emulsifying and dispersing machine, Polytron (manufactured by KINEMATICA, Switzerland). Next, inorganic dirt 14.
Add 9 g and emulsify with Polytron, then add organic dirt 3
1.35 g was added and emulsion-dispersed with Polytron to make a stable dirt bath. A predetermined 10 cm × 20 cm clean cloth (cotton cloth No. 60 designated by Japan Oil Chemistry Association) was dipped in this dirt bath, and then water was squeezed with two rubber rolls to make the amount of dirt adhered uniform. After drying this dirty cloth for 30 minutes at 105 ° C., both sides of the dirty cloth were rubbed 25 times on each side. This was cut into 5 cm × 5 cm, and the one having a reflectance within the range of 42 ± 2% was used as a soiled cloth. The soil composition of the artificial soil cloth thus obtained is shown in Table 1.

[0036]

[Table 1] Soil composition (wt% ) Organic soil: Oleic acid 28.3 Triolein 15.6 Cholesterol oleate 12.2 Liquid paraffin 2.5 Squalene 2.5 Cholesterol 1.6 Oily soil total 62.7 Gelatin 7.0 Inorganic soil 29.8 Carbon black (designated by Japan Oil and Chemical Society) 0.5

(II) Preparation of sebum cloth A cloth (cotton knitted cloth 5 × 5 cm) was coated with 60 mg of organic dirt shown in Table 1 per sheet to prepare a sebum cloth.

(III) Evaluation method The detergent composition was added to 900 ml of ion-exchanged water at 25 ° C.
It is dissolved so as to be 083%, and CaCl ₂ is added to this solution so as to be 0.0054% as CaO. 5 pieces of artificial dirt cloth (5 x 5 cm) and 3 pieces of sebum cloth were put in this, and the bath ratio was adjusted to 30 times using the washing knit cloth, and after washing for 10 minutes at 120 rpm using the tergotometer. Wash with water and dry. The reflectance of the article to be washed was measured, and the washing rate was calculated by the formula 1.

[0039]

[Equation 1]

(2) Method for evaluating cloth adhesion Black nylon slip 80g x 2 pieces Black acrylic sweater 180g x 2 pieces Blue cotton knitted shirt 100g x 5 pieces Place laundry in a jet type domestic electric washing machine and granulate Wash with detergent and tap water at 5 ° C for 5 minutes under a detergent concentration of 0.26% and a bath ratio of 30 times, then rinse with tap water at 5 ° C twice for 3 minutes each to dehydrate and wash. The amount of particles adhering to the object was visually judged according to the following criteria, and the cloth adhesion was evaluated.
The pass level is the case indicated by the symbols ◎ and ○.

⊚: No adhered particles ○: Adherent particles are not noticeable Δ: Adherent particles are slightly noticeable ×: Adherent particles are noticeable

(3) Method for measuring the rate of increase in hydrolysis The amount of anionic surfactant is determined by the methylene blue backdrop method, and the total amount M with the α-sulfofatty acid disalt is determined from the preset mixing ratio of the anionic surfactant. .. Next, the detergent composition was treated with a 90% ethanol solution having a pH of 11.50 to separate the α-sulfofatty acid di-salt as an insoluble matter, and the amount S of the di-salt was determined by the methylene blue backdrop method. Calculate the rate D.

[0043]

[Equation 2] D = (S / M) × 100% By the above operation, the hydrolysis rate immediately after the production of the detergent composition and after standing for 3 days at 60 ° C. is obtained, and the hydrolysis rate is calculated by Equation 3.

[0044]

[Formula 3] Hydrolysis rate (%) = (hydrolysis rate after 3 days)-
(Hydrolysis rate immediately after production)

[0045]

[Table 2] Sample No. 1 * ¹ 2 * ¹ 3 4 5 6 7 8 * ¹ Composition (wt%): α-SF-Na * ² 5 − 3 5 5 5 5 5 LAS-K * ³ 15 15 15 15 15 15 15 15 AOS-K * ⁴ 10 15 12 10 − 10 10 10 AS-Na * ⁵ − − − − 10 − − − Soap * ⁶ 4 4 4 4 4 4 4 4 4 Nonion * ⁷ 3 3 3 3 3 3 3 3 Silica-Na * ⁸ 1 4 4 4 4 4 4 7 Carbonate-K 10 10 10 10 10 15 20 10 Carbonate-Na 20 20 20 20 20 20 15 10 15 A-type zeolite 20 20 20 20 20 20 20 20 Fluorescence Agent 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Sulfuric acid-Na balance Moisture 6 6 6 6 6 6 6 6 Evaluation: Detergency (%) 74 69 73 75 73 75 74 75 Adhesion to cloth △ ◎ ○ ○ ○ ○ ○ O Hydrolysis increase rate (%) 5-30 25 25 20 15 60 * 1) Sample Nos. 1, 2 and 8 are comparative examples, others are Examples * 2) α-sulfo fatty acid (C ₁₄ -C ₁₆ ) methyl ester sodium * 3) linear alkyl (C ₁₄ -C ₁₆₎ potassium benzenesulfonate * 4) alpha-olefins (C ₁₄ -C ₁₆₎ sulfonated Lithium * 5) Alkyl (C ₁₂ ) sodium sulfate * 6) Fatty acid (C _{12 to} C ₁₈ ) sodium * 7) Alkyl (C ₁₃ ) ether ethoxylate (average number of moles of ethylene oxide added = 25) * 8) Na ₂ O・ 2.2 SiO ₂

Claims (1)

[Claims] 1. A sulfonic acid salt of a fatty acid lower alkyl ester having 8 to 22 carbon atoms in a fatty acid residue: 1 to 5% by weight, and (B) an anionic surfactant other than the above component (A): 1.
5 to 60% by weight, (C) silicate: 1 to 5% by weight, (D) carbonate: 10 to 40% by weight, and high in bulk density of 0.5 g / cc or more. Bulk density granular detergent composition.