KR19990047488A - Absorbent composition, low pollution powder detergent composition containing the same, and preparation method thereof - Google Patents

Abstract

The present invention relates to an absorbent composition, a powder detergent composition containing the absorbent, and a method for producing the same, wherein the biodegradable raw material is used to improve the biodegradability of the powder detergent, to uniform the size of the detergent particles, and to improve long-term stability. . The powder detergent of the present invention can improve the powder detergent which has been recognized as the main culprit of water pollution to be more suitable for the environment.

The absorbent composition of the present invention comprises 10 to 25 parts by weight of a natural anionic surfactant made from natural fats and oils and a mixture of sodium carbonate (Na ₂ CO ₃ ) and potassium carbonate (K ₂ CO ₃ ) alone or a mixture of 40 to 80 parts by weight, carbonic acid 5 parts by weight or less of sodium hydrogen (NaHCO ₃ ), 20 parts by weight or less of sodium sulfate, and 10 to 25 parts by weight of zeolite as an ion sealant.

Powder detergent composition of the present invention 30 to 80 parts by weight of the absorber; 10 parts by weight or less of powdered natural anionic surfactant; 5 to 15 parts by weight of soda ash (light); 10 to 40 parts by weight of the liquid component including a natural nonionic surfactant and aroma (1 part by weight or less); 10 to 30 parts by weight of the surface modifier.

Description

Absorbent composition, low pollution powder detergent composition containing the same, and preparation method thereof

The present invention relates to an absorbent composition, a powder detergent composition containing the absorbent, and a method for producing the same, wherein the biodegradable raw material is used to improve the biodegradability of the powder detergent, to uniform the size of the detergent particles, and to improve long-term stability. . The powder detergent of the present invention can improve the powder detergent which has been recognized as the main culprit of water pollution to be more suitable for the environment.

Laundry detergents once used phosphates to cause side effects in rivers and lakes. For this reason, phosphate has long disappeared from laundry detergents in Korea and Japan. However, the components of the detergent still contain relatively difficult to biodegrade, such as organics and polymers. Most of the organics are surfactants. Surfactants are prepared from petroleum-based raw materials and natural freights such as vegetable and animal fatty alcohols. However, the surfactant prepared from petroleum has the disadvantage of being inexpensive and poorly biodegradable. In addition, even if the surfactant produces a fatty alkyl chain from natural alcohol or the like, the biodegradation of the surfactant is less biodegradable than other substances due to the hydrophilic portion of the petroleum such as alkylbenzene and alphaolefin. In addition, polyoxyethylene glycol (PEG), carboxymethyl cellulose (CMC), polyvinyl alcohol, polyvinylpyrrolidone, poly, which are used for the purpose of preventing recontamination and dye transfer, etc. Acrylic acid or its salts, copolymers of maleic acid and vinyl ether, etc., require a long time to biodegrade by microorganisms and the like. These problems have caused water pollution when detergents are discharged into rivers.

Many methods for preparing powdered detergents for washing are known. Among them, European Patent 390251 A2 manufactures a dry powder containing a relatively large number of anionic surfactants and then pulverizes the dry powder using a mixing granulator to eliminate voids in the particles. Thereafter, liquid, slurry or powdery binders are applied to increase the density, or the dry powder is removed by the extrusion process to remove voids therein, and then pulverized to a suitable particle size to apply a liquid, slurry or powdery surface treatment agent to the surface to increase density. Is generalized.

In the above method, the content of the anionic surfactant on the dry powder is relatively high, and the amount of the liquid component such as the nonionic surfactant is very limited. Thus, the composition of the present invention can not be prepared with a relatively large amount of liquid components such as a relatively large number of nonionic surfactants to be described below.

Further, Japanese Patent No. 92-5080 discloses high density by mixing liquid surfactant, especially polyoxyethylene alkyl ether and polyoxyethylene glycol, in a dry powder prepared by petroleum-based crab surfactant through a countercurrent spray drying process. After that, a composition and process for preparing a detergent by surface modification have been developed.

In the above method, it takes a long time to be biodegradable during manufacture by using a high molecular material such as polyethylene glycol and surfactant prepared from a petroleum-based raw material, which poses a problem.

Conventional laundry detergents include anionic surfactants such as sodium alkylbenzene sulfonate, sodium alkyl sulfonate and sodium alpha olefin sulfonate, polyoxyalkylphenol ethers, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, and the like as the active ingredients. Nonionic surfactants have been mainly used, and descriptions and examples of the active ingredients are well shown in US Patent No. 3,929,678.

Examples of washing powder detergents having an anionic surfactant prepared from fatty acids and fatty alcohols as an active ingredient include US Pat. No. 4,049,586 and US Pat. No. 4,487,710. Sodium alkylbenzenesulfonate prepared from petroleum. And sodium polyoxyethylene alkyl ether sulfonate of natural fats and oils were mixed in fixed ratio. However, in the above example, surfactants prepared using alkylbenzenes, alphaolefins, and alkyl groups derived from petroleum are used as the main raw materials, so the cleaning power is excellent, but the biodegradation rate is low. Therefore, there is a high possibility of pollution problems, especially water pollution. By using the active agent has a disadvantage that the washing power is sharply dropped in hard water.

Raw materials such as polyoxyethylene alkyl ether, sodium alkyl sulfonate and sodium alkyl ether sulfonate, which are surfactants prepared from natural raw materials derived from plants and animals, have high biodegradability and are used as raw materials for low pollution detergents.

In addition, a method for preparing a low pollution high density laundry powder is shown in Korean Patent Application No. 96-77039. The above method was prepared by adding a liquid mixture such as a nonionic surfactant and polyoxyethylene glycol to a mixture of soda ash (gum ash), manganese and the like to form particles, and then modifying the surface with zeolite or the like. However, when manufactured by this method, there are many fine powders, and when washing at low temperature, especially at a temperature of 7 ° C. or less, detergents often form hydrates that do not dissolve well in water and remain in a lump form after washing. And when you look at the distribution of particles, there is a lot of fine powder, which adds to this phenomenon. In this method, the amount of liquid in the prescription is very limited, and polyoxyethylene glycol is essential for stabilizing many liquid components in the powder, which requires time for biodegradation.

The improved method than this method is the Republic of Korea Patent Application Nos. 96-71509 and 96-74799. However, they contain a large amount of liquid constituents and are excellent in particle uniformity and long-term stability, but due to the raw materials such as LAS, AOS, NP, etc., which are manufactured from high molecular weight and petroleum in the composition and have lower biodegradation rate than other components. It has the disadvantage of poor biodegradation. In addition, although the specific gravity range of the powder detergent that can be prepared by the above method is wide, it is difficult to control because the change in specific gravity during the production is made in a short time.

The present invention, as a result of the efforts to solve the above problems, excludes the petroleum-based raw materials, adding a process using an absorber in the manufacturing process based on a surfactant or a mixture prepared from plant and animal natural raw materials By adding a certain amount of soda ash (light) to the absorber, it is easier to control the specific gravity and to achieve the maximum synergistic effect as an anionic surfactant and nonionic surfactant with an appropriate amount to improve the cleaning power which is a basic property of detergent. A low-pollution laundry detergent with excellent washing power and uniform and long-term stability was obtained.

The absorbent composition of the present invention comprises 10 to 25 parts by weight of a natural anionic surfactant made from natural fats and oils or a mixture of sodium carbonate (Na ₂ CO ₃ ) and potassium carbonate (K ₂ CO ₃ ) as an alkali agent as an alkali agent or a mixture of 40 to 80 parts by weight. (In the case of a mixture, sodium carbonate / potassium carbonate> 4), 5 parts by weight or less of sodium hydrogencarbonate (NaHCO ₃ ), 20 parts by weight or less of sodium sulfate, and 10 to 25 parts by weight of zeolite as an ion sealant.

In the present invention, anionic and nonionic surfactants made from fats and oils of plants and animals are used as surfactants that are well biodegradable in preparing absorbents, and examples thereof are as follows.

First of all, as anionic surfactant

Alkylsulfonates (R ₁ -CH ₂ -SO ₃ M: R ₁ = C ₁₁ -C ₁₅ alkyl),

Polyoxyethylene alkyl ether sulfonate (R ₂ -CH ₂ -O- (CH ₂ -CH ₂ -O) n-SO ₃ M: an integer of n = 2 to 5, R ₂ = C _{9 to} C ₁₅ alkyl), And

Fatty acid salts (R ₃ -CH ₂ -COOM: R ₃ = C ₁₁ -C ₁₆ alkyl)

(Where M means a metal ion),

And as a nonionic surfactant

Fatty alcohol polyoxyethylene glycol (R ₄ -CH- (O-CH ₂ -CH ₂ ) n -OH; integer of n = 5-25, R ₄ = C ₁₁ -C ₁₈ alkyl),

Fatty acid polyoxyethylene glycol (R ₅ -CO- (OCH ₂ -CH ₂ ) m-OH; integer of m = 5-25, R ₅ = C ₁₁ -C ₁₈ alkyl),

Alkyl polyglycoside (APG) is mentioned.

This absorber is prepared in a slurry state with raw materials such as anionic surfactants, alkali agents, zeolites, and the like, and is then made into a porous material through a dryer such as a countercurrent spray dryer. This absorber serves to stably retain the liquid component inside the absorber. That is, in the present invention, the absorber is prepared by preparing a slurry with raw materials such as anionic surfactant, alkali agent, zeolite, and then drying it through a dryer such as a countercurrent spray dryer.

The absorbers thus prepared are first mixed with additives such as soda ash (fluorescent dye) and fluorescent dyes, and then have a conventional vertical or horizontal stirring shaft with a liquid component such as one or more than one nonionic surfactant (High speed mixer, Lodige mixer or Schugi mixer) and stirred to form particles of a certain size, and then the surface is coated with a surface modifier to prepare a powder detergent having excellent uniform particle size and flowability of powder and excellent long-term stability.

In other words, the absorbent of the present invention is prepared by mixing an anionic surfactant neutralized in a neutralization step with an alkali agent and an ion encapsulating agent in a ratio of 1: 2.8: 0.6 to 1: 12: 2.4 to prepare a slurry, and then drying it in a dryer.

More specifically, in the preparation of the absorbent, first, 40 to 65 parts by weight of water is added to the neutralization tank, and as much caustic soda as necessary to neutralize the anionic surfactant is added and neutralized while stirring by adding the anionic surfactant to be neutralized. At this time, as for neutralization temperature, 45-90 degreeC is preferable. After neutralization, the mixture is mixed in the form of a slurry such as additional anionic surfactant and inorganic builder. As further anionic surfactants, alkylsulfonates and polyoxyethylenealkylethersulfonates may be applied, which are commercially available in aqueous form and in powder form. Therefore, it can be applied in each form more easily. At this time, as for the temperature of a mixing tank, 45-85 degreeC is preferable. The solid content of this slurry is preferably 30 to 70 parts by weight. The solids content herein refers to the content of all substances that can solidify after drying in the slurry. Here, the content of the substance except water. After preparing the slurry, the slurry is dried using a drier such as a countercurrent spray dryer to prepare an absorbent body. In order to obtain a uniform absorbent, the viscosity of the slurry, the slurry spray rate, the size of the dryer, and the surfactant content of the slurry should be considered.

When the slurry is prepared, when the alkali agent is large compared to the amount of the surfactant, the solubility of the alkali agent in water occurs, and the alkali agent is eluted at a low temperature, thereby causing a problem in slurry injection. In addition, the viscosity change with temperature is so severe that slurry spraying is not even. On the other hand, when the amount of alkali agent is relatively low, an even absorber cannot be obtained. In addition, when the amount of zeolite applied as an ion sealant is large, the viscosity of the slurry is increased, thereby lowering the value of the solid content, thereby causing an increase in cost. On the other hand, if the amount is too small, the content of the ion-blocking agent that can be applied in the manufacture of the absorbent and powder detergent is very limited, affecting the ion-binding ability of the detergent, as well as the deterioration of the washing power in hard water as well as the viscosity change of the slurry is severe. This is because fine powders such as ion sealants have a property of maintaining slurry viscosity.

The apparent density of the absorber obtained in the present invention is 0.35 to 0.8 g / cm 3.

The absorber prepared by this method, soda ash (light), liquid components including nonionic surfactants, and surface modifiers are mixed at a ratio of 8: 1: 1 to 2.2: 2: 1, and the liquid component is impregnated with the absorber in a mixing tank. In addition, the surface is modified with a surface modifier to prepare a powder detergent.

Powder detergent composition according to the invention the absorber 30 to 80 parts by weight; 10 parts by weight or less of powdered natural anionic surfactant; 5 to 15 parts by weight of soda ash (light); 10 to 40 parts by weight of a liquid component including a natural nonionic surfactant and fragrance (1 part by weight or less), 10 to 30 parts by weight of at least one surface modifier selected from among zeolite, clay and talc.

More specifically, the powder detergent composition may contain 30 to 80 parts by weight of the absorbent, an alkyl sulfonate or polyoxyethylene alkyl ether sulfonate which is a powdered anionic surfactant, or 10 parts by weight or less of a mixture, and 5 to 15 fine powders such as soda ash (light). After adding the optical brightener with parts by weight and additives, the mixture is stirred, and then 10 to 40 parts by weight of liquid components such as nonionic surfactants and fragrances (fragrance is 1 part by weight or less) are sprayed in a vertical and horizontal high speed rotary granulator. To form. At this time, the particles are uniform in size, but the surface of the particles is slightly moistened while the absorber is impregnated with a large amount of liquid components. However, by coating with 10 to 30 parts by weight (more suitable to 15 to 25 parts by weight) of the surface modifier, it is possible to prepare detergent particles having a uniform particle size and excellent long-term stability. And when the detergent is made in this process, depending on the granulator, each time the liquid component is impregnated and coated has a great influence on the flow properties of the powder particles. If the process of impregnating the liquid component is short, the liquid component is not properly impregnated into the absorber, so that the surface modifier is separated from the absorber and the liquid component is added, not only even distribution of the components but also causes problems such as long-term stability. On the contrary, if the process time is too long, the impregnated liquid component flows out and aggregates among the particles to generate lumps. This makes it difficult to have an even distribution of components and leads to an increase in the content of surface modifiers. In addition, if the time for coating the particles impregnated with the liquid component with the surface modifier is short, the particles and the surface modifier are not properly coated, and are separated from each other.

In addition, by adding a small amount of fine powder such as soda ash (light) with the absorber, it is easy to control the impregnation time of the liquid raw material in the production of powder detergent, thereby achieving the efficiency of production. Because the fine powder and the absorbent, such as soda ash, respectively differ in the time and amount of impregnating the liquid raw material, it is possible to improve the production efficiency in the range between the fine powder and the absorbent, such as soda ash of the present invention. The weight ratio between the fine powder and the soda ash as the absorbent in the present invention is 2: 1 to 16: 1.

The powder detergent of the present invention thus prepared has an apparent density of 0.5 to 1.3 g / cm 3, and a gradient of particle size is given in the Examples.

As the surface modifier, it is preferable to use at least one selected from powder zeolite, talc, clay and silica. Among them, powder zeolite is preferred. And although the surface modifier is somewhat different depending on the type, it is preferable to contain a particle size of less than 10 ㎛ 50% by weight or more.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, these examples are only for illustrating the present invention, and the scope of the present invention in any sense is not limited by these examples.

<Examples 1 to 4 and Comparative Examples 1 and 2>

Comparative Example 1

Next, a detergent slurry (solid content: 60 wt%) containing a detergent composition having the ingredients and contents shown in Table 1 was sprayed downward from the top of the countercurrent spray drying tower to prepare a powder powder of a bead.

Detergent composition Content (% by weight) Straight chain alkylbenzene sulfonate 15.0 Sodium alpha olefin sulfonate 14.0 Sodium fatty acid 3.5 Sodium carbonate 30.0 Sodium silicate 10.0 Carboxymethyl Cellulose 1.0 Powder Zeolite 4A 19.0 * Fluorescent dyes 0.5 Alkyl sulfate (C ₁₂ -C ₁₄ ) 3.0 Oxo alcohol polyethylene glycol ether 4.0

* Fluorescent dye stilbene: Tinopal AMX-GX from Ciba Geigy

Comparative Example 2

Next, the detergent composition having the ingredients and contents shown in Table 2 was added to a mixture of alkalis, etc. without undergoing a drying process, and then particles were formed to form particles and then modified using a surface modifier to prepare a powdered powder detergent.

Detergent composition Content (% by weight) Fatty alcohol polyoxyethylene glycol 17.0 Sodium fatty acid 9.0 Polyoxyethylene glycol 2.0 Soda ash 30.2 sulphate of soda 10.0 Sodium Silicate 1.0 Powder Zeolite 4A 30.0 * Fluorescent dyes 0.5 incense 0.3 Carboxymethyl Cellulose 1.0

* Fluorescent dye stilbene: Tinopal AMX-GX from Ciba Geigy

Surfactant prepared from natural fats and oils

Examples 1-4

Next, as described above, the absorbent was first prepared from the detergent raw materials shown in Table 3, and then liquid powder was added and treated with a surface modifier to obtain a powder detergent.

(Unit: weight%) Tax material Example One 2 3 4 Remarks One Sodium Fatty Acid 10 10 10 10 Absorber composition 2 Sodium alkyl sulfonate 10 7 3 - 3 Sodium polyoxyethylene alkyl ether sulfonate - 3 7 10 4 Soda society (middle) 45 45 45 45 5 Sodium sulfate 10 10 10 10 6 Powder Zeolite 4A 25 25 25 25 7 Absorber 47.5 47.5 47.5 47.5 Three manufacturing castles 8 Soda Sashimi 6 9 12 15 9 ^* Nonionic surfactant 25 22 19 16 10 Powder Zeolite 4A 20 20 20 20 11 ^* Fluorescent Whitening Agent 0.5 0.5 0.5 0.5 12 ^* Other additives One One One One

9 ^* : fatty alcohol polyoxyethylene glycol (AE-7 Ilchi Chemical)

11 ^* : Tinopal AMX-GX of fluorescent dye stilbene-Chiba Geigy Corporation

12 ^* : fragrance, enzyme, etc.

★: surfactant prepared from natural fats and oils

Experimental Example 1: Physical Properties of Powder Detergent According to the Present Invention

Powder detergents prepared according to Comparative Examples and Examples were evaluated for fluidity under the following conditions.

1) Liquidity Evaluation

The fluidity of each powder detergent was compared by measuring the time it took to pass through the funnel with 100 cc of powder having a top diameter of 10 cm and an inner diameter of the bottom tube of 7 mm.

Test results for detergency and fluidity are shown in Table 4, along with the apparent density and surfactant content of the powder detergent.

division Comparative example Example One 2 One 2 3 4 One Fluidity (sec) 21-23 20-21 20-21 16-18 16-17 14-15 2 Surfactant Content (% by weight) 39.5 28 34.5 31.5 28.5 25.5 3 Apparent density of absorber (g / cm3) 0.35 - 0.47 0.44 0.44 0.41 4 Apparent density of powdered detergent (g / cm3) 0.62 0.81 1.12 0.91 0.82 0.75

2) Particle size distribution comparison

In Table 5, 200 g of the powder is divided into 200 by measuring the remaining amount in each sieve by using a shaker for 10 minutes from 12 mesh to 100 mesh 10 sieves.

Unit: percentage division Comparative example Example One 2 One 2 3 4 12 mesh unopened 5.1 3.2 2.4 1.8 1.8 1.0 14 mesh not passed 6.2 5.8 6.5 5.7 5.5 6.1 18 mesh unpassed 7.1 5.5 9.2 10.1 11.4 10.8 20 mesh unpaid 8.3 10.2 17.1 15.4 16.4 15.7 25 mesh not passed 9.8 9.6 18.6 18.1 14.9 15.2 30 mesh not passed 14.9 7.9 16.9 20.3 21.4 20.6 40 mesh unopened 8.4 8.3 22.4 18.5 17.5 18.2 50 mesh unopened 3.7 10.0 5.4 7.8 8.4 8.7 60 mesh unopened 4.3 7.1 1.4 1.1 1.4 2.1 100 mesh not passed 11.1 13.0 0.1 1.1 1.1 1.2 100 mesh passes 21.0 19.4 - 0.1 0.2 0.4

3) Long-term stability test

In Table 6, the specimens of Comparative Example and Example were stored in a sealed container in a width × length × height (24 cm × 10 cm × 33 cm) size container at a temperature of 40 ° C. and a relative humidity of 80%. When fluidity changes over time.

Unit: (sec) time 1 day 3 days 1 week 2 weeks 3 weeks 1 month 2 months 3 months Comparative Example 1 21-23 25-27 28-30 35-38 Not measurable Not measurable Not measurable Not measurable Comparative Example 2 20-21 22-24 26-27 27-29 28-30 28-31 29-31 30-32 Example 1 20-21 20-21 22-24 26-27 26-29 27-30 28-30 29-32 Example 2 16-18 18-19 20-21 22-24 24-25 26-28 28-29 28-30 Example 3 16-17 16-17 18-19 21-222 22-25 23-25 25-26 25-26 Example 4 14-15 14-16 15-16 16-18 19-21 22-23 22-24 23-25

4) Evaluation of cleaning power

Washing power experiment was carried out under the following conditions with the prepared comparative examples and examples to obtain the washing power of the comparative examples and examples using the following formula and the results are shown in Table 7 below.

Laboratory equipment: Terg-O-Tometer

Hardness of water: 80 ppm hard water (Ca ++, 20 ppm Mg ++)

Temperature of water: 25 ℃

Bath ratio: 4.5 g / washing water ℓ

Detergent concentration: Comparative Example-1- (0.67 g / L), Comparative Example-2- and Example (0.67 g / L, 0.5 g / L)

Contaminated fabric: EMPA Art No. 102 (olive oil, carbon black / blend (polyester / cotton))

Ro: surface reflectivity of the fabric before contamination

Rs: Surface reflectivity of contaminated cloth

Rw: surface reflectivity of contaminated cloth after cleaning

Unit: percentage division Comparative example Example One 2 One 2 3 4 Detergency (0.67 g / ℓ) 65 78 87 85 80 76 Detergency (0.5 g / ℓ) - 67 72 71 69 66

5) Biodegradation Evaluation

Prepared Comparative Examples and Examples are shown in Table 8 by measuring the biodegradation by KS M 2714 (92).

percentage division Comparative example Example One 2 One 2 3 4 Days 1-2 40.1 91.4 99.2 99.3 99.3 99.5 Days 7-8 97.8 99.7 99.9 or more 99.9 or more 99.9 or more 99.9 or more

As can be seen from the results of Tables 4 to 8, the powder detergent (Examples 1 to 4) according to the present invention showed excellent performance even in long-term stability as well as excellent uniformity and fluidity of the powder particles compared to the conventional powder detergent. . The problem of washing power was also superior to that of conventional detergents, and in particular, in terms of biodegradability, very superior results were obtained.

Therefore, when the powder detergent is prepared by the method of the present invention, it is possible to obtain a product of excellent quality and to contribute to the solution of water pollution.

Claims (4)

10 to 25 parts by weight of a natural anionic surfactant made from natural oils and 40 to 80 parts by weight of a mixture of sodium carbonate (Na ₂ CO ₃ ) and potassium carbonate (K ₂ CO ₃ ) alone or as a mixture, sodium hydrogen carbonate (NaHCO ₃ ) An absorbent composition for preparing a powder detergent containing 5 parts by weight or less, 20 parts by weight or less of sodium sulfate, and 10 to 25 parts by weight of zeolite as an ion sealant. The absorbent composition of claim 1, wherein the alkali agent is a mixture of sodium carbonate and potassium carbonate and wherein sodium carbonate / potassium carbonate> 4. 30 to 80 parts by weight of the absorbent made of the composition of claim 1; 10 parts by weight or less of powdered natural anionic surfactant; 5 to 15 parts by weight of soda ash (light); 10 to 40 parts by weight of the liquid component including a natural nonionic surfactant and aroma (1 part by weight or less); Powder detergent composition containing 10 to 30 parts by weight of the surface modifier. The water absorbent of claim 1, soda ash (light), a liquid component including a nonionic surfactant, and a surface modifier are mixed at a ratio of 8: 1: 1 to 2.2: 2: 1, and when mixed, the weight ratio between the absorber and soda ash is 2: 1. To 16: 1, wherein the absorbent body is impregnated with a liquid component in a mixing tank, and the surface detergent is prepared by using a surface modifier.