KR100420105B1 - Laundry Detergent Composition - Google Patents

Abstract

The present invention comprises 75 to 90% by weight of powder consisting of sodium sesquicarbonate and layered silicate (hereinafter, based on the total weight of the composition), 5 to 10% by weight of surfactants and other laundry detergents in a weight ratio of 65:35 to 95: 5. It relates to a laundry detergent composition consisting of 100% by weight of additives commonly used in the composition. The composition of the present invention provides a pollution-free detergent that minimizes the amount of surfactant while the cleaning power is comparable to or rather increased with existing detergents.

Description

Laundry Detergent Composition

The present invention relates to a laundry detergent composition. More specifically, the present invention relates to an environmentally friendly, non-toxic laundry detergent composition that exhibits excellent cleaning power even when a small amount of surfactant is contained using only sodium sesquicarbonate and layered silicates without using phosphoric acid and zeolite as a builder.

Laundry detergents are a major requirement for good cleaning performance of laundry and must not be polluted by the wash residue. Due to these requirements, the development of pollution-free detergents is actively underway. For example, detergents using vegetable surfactants and detergents using waste oils have been developed. However, since the vegetable surfactant is difficult to extract from the plant, there is a problem that a sufficient amount cannot be secured. In addition, there is a problem that the detergent using waste oil is not easy to use because it can not be made into a powder form. For this reason, research on pollution-free detergents has been conducted in part toward reducing the content of surfactants and maximizing the performance of builders. Korean Patent Publication No. 2001-0082782 discloses sodium tripolyphosphate in which a cationic, anionic and / or nonionic surfactant is used at about 10% to 45% based on the total weight of the detergent composition and is a phosphorus compound. , 4A zeolite of aluminosilicate system, sodium nitrilotriacetate, sodium carbonate, sodium bicarbonate, sodium sesquicarbonate, sodium sulfate, sodium silicate, layered silicate It is mentioned that builders such as Burkeite, Citrate and the like are used at about 35-75% based on the total weight of the detergent composition.

Builders that are in the spotlight in pollution-free detergent research are sodium sesquicarbonate and layered silicates. Sodium sesquicarbonate has several advantages. In particular, it is characterized by excellent cleaning power and pollution-free. And exhibits an alkaline pH, which minimizes fiber damage. In general, layered silicates have a structure having a two-dimensional sheet and this layer is called a δ-layered structure. Inorganic ions of various sizes can be exchanged between the layers and the organic polymer can be inserted into the layer, thus showing the ability to remove hardness components in water and excellent adsorption properties for contaminants during washing. It has suitable physical properties for the furnace. In addition, since the oil absorption properties for the surfactant is excellent, there is a feature that can reduce the amount of the surfactant used in the formulation of the detergent. In particular, when the layered silicate is used as a detergent builder, the commercialization of sodium tripolyphosphate (STPP) is restricted, and the pupil size, which is a disadvantage of the aluminosilicate zeolite A, which has been frequently used as the detergent builder, is fixed to the calcium ion among the hardness components in water It has excellent removal ability, but it has little removal ability for large hydration ions such as magnesium ions, and alkali-induced zeolite particles are deposited in the fiber gap due to insolubility in water. It may affect the human body, it is deposited in the operating part of the washing machine can solve the problems that can trigger the wear of the washing machine has been spotlighted as an alternative material. In addition, it is attracting attention as a detergent supplement that can contribute to environmental protection by being able to manufacture compact detergent which is a global trend.

As described above, these ingredients are known as next-generation detergent auxiliaries in that they have excellent cleaning power and are non-polluting and have been proposed as a component of detergents in many documents. U.S. Patent 5,756,445 discloses a granular detergent composition comprising 20-50% by weight of aluminosilicate (low bulk density component) and a mixture of 10-50% by weight of layered silicate and sesquicarbonate (high bulk density component). Is disclosed. British Patent 2315762 describes detergent compositions comprising sesquicarbonates and / or layered silicates as an alkaline source with dicarboxylic acids. The Republic of Korea Patent Publication No. 2001-0082782 describes a detergent composition comprising a powder containing a large amount of sesquicarbonate obtained from sodium bicarbonate, anhydrous soda ash, water, synthetic surfactant, silica, sodium silicate, neutral salt, polymer dispersant have.

The inventors reacted by mixing each aqueous solution homogenized with sodium bicarbonate and sodium silicate together, drying the resulting slurry to produce a powder, and analyzing the resulting powder by XRD. The powder was very surprisingly the layered silicate and sodium In particular, the detected sodium sesquicarbonate exhibits high quality in terms of crystal structure, particle size and density even without using a seed nucleus or anionic surfactant. (Scanning electron microscopy), and a method for simultaneously preparing sodium sesquicarbonate and layered silicate was filed with the Korean Patent Office on January 23, 2002 and is pending in the application number 10-2002-0003998.

SUMMARY OF THE INVENTION An object of the present invention is to provide a detergent composition for washing laundry that is excellent in cleaning power and environmentally friendly while minimizing the amount of surfactant by using only layered silicate and sodium sesquicarbonate as builders without using other kinds of builders.

The present invention comprises 75 to 90% by weight of powder consisting of sodium sesquicarbonate and layered silicate (hereinafter, based on the total weight of the composition), 5 to 10% by weight of surfactants and other laundry detergents in a weight ratio of 65:35 to 95: 5. It provides a laundry detergent composition consisting of 100% by weight of additives commonly used in the composition.

1 is an XRD analysis graph of a powder sample prepared according to the method of the present invention.

2 is a SEM photograph of a powder sample prepared according to the method of the present invention.

Sodium sesquicarbonate and the layered silicate used in the laundry detergent composition of the present invention can be used according to the invention developed by the present inventors and pending in the pending Korean Patent Application No. 10-2002-0003998. Starting materials used to prepare sodium sesquicarbonate and layered silicates are sodium bicarbonate and sodium silicate.

Heavy baths are usually prepared by carbonation of aqueous sodium carbonate (Na ₂ CO ₃ ) (RN Shreve et al., Chemical Process Industries, McGraw-Hill Book Co., 4th ed., 1977, p.213 ). In commercial sodium bicarbonate manufacturing, first, a soda ash (a hydrated mineral composed mainly of Na ₂ CO ₃ ) is dissolved in an aqueous solution, and then a saturated soda ash solution is placed in a carbonation container and contacted with carbon dioxide gas and cooled simultaneously. Recovered as an aqueous slurry in a carbonation vessel, filtered and then dried to obtain sodium bicarbonate crystals. In addition, sodium bicarbonate can be prepared from a trona ore (crude sodium sesquicarbonate) through a multistage purification process. Such manufacturing methods are described in US Pat. Nos. 2,346,140, 2,639,217, 3,028,215, 3,780,160, 6,207,123, 200/0001037 and Chinese Patent 1270926.

Sodium silicate is a material obtained by reacting a mixture of silica and soda ash or caustic soda at 1200 ° C. or higher. It is composed of SiO ₂ and Na ₂ O and forms various compounds according to the composition ratio of the two materials. The amorphous silicates are largely divided into crystalline and amorphous forms. Sodium metasilicate having a SiO ₂ : Na ₂ O molar ratio of 1: 1, sodium orthosilicate having a 1: 2, and sodium sesquisilicate having a 2: 3 ( sodium sesqu isilicate), and as the ratio of SiO ₂ increases from 2 to 4, there are 1 to 4 types of sodium silicates in liquid phase containing 30 to 50% water. Commercially available liquid sodium silicate has a SiO ₂ : Na ₂ O ratio of about 2 to 4: 1. The SiO ₂ : Na ₂ O ratio of sodium silicate which can be preferably applied is in the range of 2.1 to 3.8: 1.

The method according to the invention can increase the yield by preventing the formation of lumps that can interfere with the process by controlling the amount of moisture during the process. In a preferred embodiment, the ratio of solids and moisture in the mixture of sodium bicarbonate and sodium silicate is maintained at about 50-70%. In this regard, since sodium silicate contains its own moisture, the amount of water added directly is less than about 50-70% of the total. Less moisture can produce a lot of anhydrous soda ash. On the other hand, excessive moisture can inhibit the reaction of sodium silicate with sodium bicarbonate. In other words, sodium silicate and sodium bicarbonate react with each other on its own, so that sodium silicate is a transparent crystal and sodium bicarbonate is dissolved in water.

By reacting the aqueous sodium bicarbonate solution with an aqueous sodium silicate solution and drying the reaction solution, a powder composed of sodium sesquicarbonate and layered silicate used in the detergent composition of the present invention is obtained (FIG. 1). The resulting sodium sesquicarbonate is represented by the empirical formula of NaCO ₃ · NaHCO ₃ · 2H ₂ O, which is a crystal having a needle-like structure in the powder state. The resulting layered silicate can be represented by the general formula of NaMSi _x O _{2 + 1} yH ₂ O where M is sodium (Na) or hydrogen (H) and x is 1.9 to 4 and y is 0 to 20. have.

In the process according to the invention, the temperature conditions are preferably about 100 ° C. or higher when the aqueous sodium bicarbonate solution is reacted with the aqueous sodium silicate solution. This is because the yield of layered silicate can be significantly reduced when the reaction temperature is about 100 ° C or lower. On the other hand, when the temperature condition is about 150 ° C. or more, layered silicates are produced but sodium sesquicarbonate may be decomposed. In this respect, the preferred reaction temperature of the aqueous sodium bicarbonate solution and the aqueous sodium silicate solution is in the range of about 100 ° C to about 150 ° C. The reaction time of the aqueous sodium bicarbonate solution and the aqueous solution of sodium silicate may vary depending on the temperature conditions, and a suitable time can be easily determined by repeating the experiment in a range that does not impart experiment burden to those skilled in the art. As a preferred embodiment of the present invention, a high yield can be obtained when reacting at 125 ° C. for 1 hour to 1 hour 30 minutes. The slurry of sodium bicarbonate and sodium silicate mixed according to the process of the present invention can be dried by simply heating. Other drying methods include spray and belt type, both of which are well known in the art and may be preferably used in the present invention.

The heating reaction in aqueous solution of sodium bicarbonate and sodium silicate takes place as follows. First, the sodium bicarbonate is reacted as in Schemes 1 and 2 below.

NaHCO ₃ → Na ⁺ + HCO ₃ ^_

2HCO ₃ ^_ → H ₂ O + CO ₂

The above reaction does not occur well in aqueous solution at room temperature, but the reaction occurs actively at 60 ° C. or higher. CO ₂ generated in Schemes 1 and 2 reacts with sodium silicate as follows. The CO ₂ produced here is an important component leading to Scheme 3.

Na ₂ O ₂ SiO ₂ + CO ₂ + 4 H ₂ O → Na ₂ CO ₃ + ₂ Si (OH) ₄

Na ₂ CO ₃ reacts with water to form Na ₂ CO ₃ · H ₂ O.

_{Na 2 CO 3 + H 2 O} → Na 2 CO 3 · H 2 O

Na ₂ CO ₃ · H ₂ O obtained in Scheme 3 reacts with NaHCO ₃ not in Schemes 1 and 2

_{Na 2 CO 3 · H 2 O} + NaHCO 3 + H 2 O → Na 2 CO 3 · NaHCO 3 · 2H 2 O

Becomes

Sodium sesquicarbonate is produced in Scheme 5, and the sum of Schemes 4 and 5 is as follows.

_{Na 2 CO 3 + NaHCO 3 +} 2H 2 O → Na 2 CO 3 · NaHCO 3 · 2H 2 O

Si (OH) ₄ generated in Scheme 3 is very unstable and combines with other Si (OH) ₄ to form disilicic acid.

Disilicate in Scheme 7 combines with Na ⁺ ions present in excess in Scheme 1 to form a layered silicate. At this time, when the temperature is 100 ° C. or less, no layered silicate is produced. In this reaction, when anhydrous soda ash is mixed, an excess of soda ash together with soda ash coming out of sodium silicate on the reaction mechanism is generated in an excess amount of anhydrous soda ash that does not participate in sodium sesquicarbonate bond. And the probability of the reverse reaction of Scheme 3 is increased.

Alternatively, the sodium bicarbonate and sodium silicate may be mixed with each other and then mixed with each other, or the sodium bicarbonate and sodium silicate may be put together in water before the reaction is performed. However, this method can make the process difficult and increase the yield if the capacity is increased.

Sodium sesquicarbonate and layered silicates according to the invention are used in amounts of 75% to 90% based on the total weight of the detergent composition of the invention. At this time, the ratio of sodium sesquicarbonate and the layered silicate is used in the range of 65:35 to 95: 5 by weight. The powder composed of sodium sesquicarbonate and layered silica prepared according to the method has a ratio of sodium sesquicarbonate and layered silicate in the range of about 65:35 to 95: 5.

Surfactants used in the detergent composition of the present invention include soap-based, anionic and / or nonionic surfactants. The amount of these surfactants is 5 to 10% based on the total weight of the detergent composition. If the surfactant is used at 5% or less, the action of the surfactant is weak and satisfactory washing power cannot be obtained. The amount of the surfactant may be 10% or more, but from the viewpoint of environmental friendliness and pollution-free, in the present invention, the range is preferably 10% or less, more preferably 7% or less, and sodium specifically used according to the present invention. Sesquicarbonate and layered silicate provide sufficient cleaning power even when the surfactant is used in an amount of 10% or less, and in addition, the cleaning power obtained by using the surfactant in the range of 5 to 10% according to the present invention even when 10% or more of the surfactant is used. It has been found that no particularly improved cleaning power can be expected in comparison with the above.

Examples of anionic surfactants include, but are not limited to, straight chain alkylsulfonates (Rn-CH ₂ -O-SO ₃ Na n = 12-16), alkanesulfonates (Rn-SO ₃ -Na n = 12-18). ) And an alpha olefin sulfonate (Rn1-CH = CH-Rn2-SO ₃ Na), or a mixture of two or more thereof, and the amount thereof is 1 to 10% based on the total weight of the detergent composition. . Since most of the anionic surfactants contain sulfur components, it is preferable to use them in the smallest amount possible, for example, 3% or less, since they are protein-modified or toxic, causing environmental friendliness and nontoxicity.

Nonionic surfactants include, but are not limited to, polyoxyethylene (POE) amines, POE fatty acid esters, polyethylene glycols, polyethylene glycol fatty acid esters, polyoxyethylene fatty acid alcohol ethers, and condensates of polyoxyethylene and polyoxypropylene. And sorbitan fatty acid ester compounds. Its use amount is 3 to 10% based on the total weight of the detergent composition.

Preferably, more amount of nonionic surfactant is used compared to the amount of anionic surfactant. The reason is that even when the anionic surfactant is rinsed to some extent, it has been reported that it affects the human body, and in fact, the nonionic surfactant has a superior cleaning power than the anionic surfactant.

Soap based surfactants include, but are not limited to, fatty acids with (RnCH ₂ -CO ₂ Na n = 8-18) and the amount used in the detergent composition is 2-5% based on the total weight of the detergent composition. to be. Soap surfactant is environmentally friendly using a natural raw material, but the cleaning power is poor, so the amount can not be used a lot and it is preferable to use with other surfactants.

The detergent composition of the present invention may further use bleach, enzyme, dispersant (acrylic system), perfume, etc. in an amount of at least 5% by weight, as much as 20% by weight, and the amount of each of these components is well known to those skilled in the art.

The bleaching agent is hydrogen peroxide, such as using a oxidizing there is an intensive oxidizing bleaching agent to the bleaching action sodium percarbonate _{(2Na 2 CO 3 · 3H 2} O 2) and sodium perborate _{(NaBO 2 · H 2 O 2} · 3H 2 O) ( H ₂ O ₂ ), mainly sodium percarbonate.

Enzymes used are neutral and alkaline proteases, lipases, cutinases, esterases, amylases, pectinases, lactases, peroxidases and cellulases. Proteases can be used that are commercially available to play a role in breaking down protein contamination in the body. Commercial proteases include Primase (Novo Industries A / S), Maxapem (Gist-Brocades) and Optimase and Opticlean (Solvay Enzymes). The amount of protease used is approximately 0.0001 to 3% based on the total weight of the detergent composition. Lipase breaks down fat from the body and can be obtained from fungi and bacteria such as Humicola species, Thermomyces species or Pseudomonas species. Moreover, what is marketed can be used. An example of such a lipase commercial item is Lipolase (Novo Industry A / S). The amount of lipase used is about 0.0001 to 2% based on the total weight of the detergent composition. Amylase breaks down externally contaminated starch species. Amylases that may be used include, but are not limited to, commercial Rapidase (Gist-Brocades) and Termamyl and BAN (Novo Industries A / S). Finally, cellulase breaks down the fibers and removes lint from natural cotton garments. Cellulase useful in the present invention preferably includes both bacterial and fungal types with a pH optimum of 5 to 9.5. U.S. Patent No. 4,435,307 discloses cellulase 212 produced by fungi belonging to the genus Fungal Cellulase or Aeromonas from Humicola insolens or Humicola strain DSM 1800 and Dolabella auri, a marine mollusc. Cellulase extracted from the liver pancreas of Dolabella Auricula Solander is described as suitable. Suitable cellulases are also described in UK 2,075,028, UK 2,095,275 and German OS 2,247,832. All these cellulase can be used in the detergents of the present invention.

Dispersants include, but are not limited to, acrylic polymer systems and have high effects in hard water softening, dispersibility, detergency, biodegradability, and heavy metal chelation. The amount of the dispersant used is about 0.0001 to 2% based on the total weight of the detergent composition.

Detergent compositions according to the invention can take several physical forms, including powder, granular, tablet, bar and liquid forms. Such formulations can be readily prepared according to conventional techniques in the detergent field.

The liquid detergent composition may contain other solvents such as water and carriers. Low molecular weight primary or secondary alcohols (eg methanol, ethanol, propanol and isopropanol) are suitable. Monohydric alcohols are preferred for soluble surfactants, but also polyols having about 2 to 6 carbon atoms and about 2 to 6 hydroxyl groups (eg, 1,3-propanediol, ethylene glycol, glycerin and 1,2-propane). Diol) can be used. Carriers may be used in the range of 5 to 90%, typically 10 to 50%, based on the composition. The detergent composition of the present invention is preferably formulated as above while used for aqueous washing, and the wash water has a pH of about 6.5 to about 11, preferably about 7.5 to about 10.5. Laundry products typically have a pH of 9-11. Techniques for adjusting pH at recommended dosage levels include the use of buffers, alkaline acids, and the like, which are well known to those skilled in the art.

The invention will be more specifically illustrated by the following examples. However, these examples are merely embodiments of the invention and do not limit the scope of the invention.

Raw material manufacturing

<Example 1>

Mix 150 ml of water with 273 g of sodium bicarbonate to make a uniform mixture, and mix 750 ml of water with 727 g of one kind of sodium silicate (SiO ₂ : Na ₂ O = 2.11: 1) in a reactor at 125 ° C. for 1 hour 30 minutes. Reaction gave a slurry having a water content of 50 to 70%. This slurry was dried to produce a white powder.

<Example 2>

200 ml of water was mixed with 345 g of sodium bicarbonate to make a uniform mixture. 655 g of one kind of sodium silicate (SiO ₂ : Na ₂ O = 2.11: 1) was mixed with 750 ml of water at 125 ° C. for 1 hour 30 minutes. Reaction gave a slurry having a water content of 50 to 70%. This slurry was dried to obtain a powder.

<Example 3>

376 g of sodium bicarbonate was mixed with 300 ml of water to make a uniform mixture, and 624 g of one kind of liquid sodium silicate (SiO ₂ : Na ₂ O = 2.11: 1) was mixed with 750 ml of water and reacted at 125 ° C. for 1 hour and 30 minutes in a reactor. To obtain a slurry having a water content of 50 to 70%. This slurry was dried to give a powder.

Example 4

A mixture of 300 ml of water and 429 g of sodium bicarbonate was added to form a homogeneous mixture. 600 ml of water was mixed with 571 g of one kind of sodium silicate (SiO ₂ : Na ₂ O = 2.11: 1), and the reactor was stirred at 125 ° C. for 1 hour 30 minutes. Reaction gave a slurry having a water content of 50 to 70%. This slurry was dried to produce a powder.

Example 5

385 g of sodium bicarbonate was mixed with 300 ml of water to make a uniform mixture. 700 ml of water was mixed with 615 g of _two liquid sodium silicates (SiO ₂ : Na ₂ O = 2.35: 1) and reacted at 125 ° C. for 1 hour and 30 minutes in a reactor. To obtain a slurry having a water content of 50 to 70%. This slurry was dried to produce a powder.

<Example 6>

200 ml of water is mixed with 357 g of sodium bicarbonate to make a uniform mixture, and 700 ml of water is mixed with 643 g of three liquid sodium silicates (SiO ₂ : Na ₂ O = 3.21: 1) at 125 ° C. for 1-2 hours in a reactor. Reaction gave a slurry having a water content of 50 to 70%. This slurry was dried to produce a powder.

<Example 7>

200 ml of water was mixed with 332 g of sodium bicarbonate to make a uniform mixture. 700 ml of water was mixed with 668 g of four liquid sodium silicates (SiO ₂ : Na ₂ O = 3.76: 1) at 125 ° C. in a reactor for 1 hour 30 minutes. Reaction gave a slurry having a water content of 50 to 70%. This slurry was dried to produce a powder.

Experimental Example 1

The powders prepared in Examples 1 to 7 were found to have about 65% to 95% sodium sesquicarbonate and about 5% to 35% layered silicates.

Detergent composition preparation

Washing compositions were prepared using the ingredients and compositions described in Table 1 below.

Table 1

Detergent composition (% by weight) Comparative example Example One 2 3 4 One 2 3 4 Dry Powder (1) - - - - 87.4 80.4 76.5 85.9 Sodium carbonate 25 18 42 42 - - - - Zeolite 25 10 30 30 - - - - STPP - 15 14 - - - - - Sodium Silicate - 6.7 - - - - - - Sodium alkylbenzenesulfon (2) 14 24 - 5 8 - - - Fatty acid salts (3) 3 - 5 5 - 2 2 2 Nonionic Surfactant (4) 2 - 6 - 2 3 8 3 Sodium sulfate 30 18.3 - 15 - - - - Other additives (5) One 8 3 3 2.6 14.6 13.5 9.1 (1) Powder consisting of sodium sesquicarbonate and layered silicate (2) Fatty acid salts having 12 to 16 carbon atoms (3) Alkyl groups extracted from natural alcohols (4) Polyoxyethylene fatty acids extracted from natural fatty acids Ethers (5) bleaches, flavorings and dispersants

Laboratory Example 2

The detergency of the detergent composition was evaluated using the following instruments and conditions.

Cleaner: Terg-o-tometer

Washing temperature: 20 ℃

Washing water: Hardness Ca ²⁺ 80ppm Mg ²⁺ 20ppm

Bath ratio: 4.3 g / l (stained cloth / wash water)

Pollutant: CFT AS-9 (pigment / oil)

Detergent concentration: 0.67 g / ℓ

Evaluation: Conversion of Comparative Example 1 as 100

The test results are shown in Table 2 below.

TABLE 2

Comparative example Example One 2 3 4 One 2 3 4 Washing power 100 109 105 109 107 108 114 109

The composition containing the powder consisting of sodium sesquicarbonate and layered silica in accordance with the present invention provides a pollution-free detergent that has a cleaning power comparable to or rather increased than conventional detergents while minimizing the amount of surfactant.

Claims (6)

75 to 90% by weight of powder consisting of sodium sesquicarbonate and layered silica (hereinafter, based on the total weight of the composition), 5 to 10% by weight of surfactants and other laundry detergents in a weight ratio of 65:35 to 95: 5 Laundry detergent composition consisting of 0 to 20% by weight of the additive used. The method of claim 1, wherein the powder consisting of sodium sesquicarbonate and layered silicate is (a) an aqueous solution of sodium silicate is mixed with a sodium bicarbonate aqueous solution prepared separately, to generate a reaction solution, and (b) the reaction solution is heated. Reacting to form a slurry, and (c) drying the formed slurry to produce a powder. The method of claim 1, wherein the powder consisting of sodium sesquicarbonate and layered silicate is (a) a mixture of sodium silicate and sodium bicarbonate together with water to form a reaction solution, and (b) the reaction solution is heated to react the slurry. And (c) drying the formed slurry to produce a powder. The composition of claim 2 or 3, wherein the SiO ₂ : Na ₂ O ratio of sodium silicate in step (a) is from 2.1: 1 to 3.8: 1. The composition according to claim 2 or 3, wherein the composition is heated to a temperature of 100 to 150 ° C in step (b). The composition of claim 2 or 3, wherein in step (b) the slurry has a water content of 50 to 70%.