KR100516488B1 - Manufacturing method of nonionic absorbent and manufacturing method of fabric softener-containing detergent using same - Google Patents

Abstract

The present invention is 30 to 80% by weight of one or more mixtures selected from the group consisting of sodium carbonate (Na ₂ CO ₃ ), sodium bicarbonate (NaHCO ₃ ) and sodium sulfate (Na ₂ SO ₄ ), 0 to 40% by weight of water-insoluble minerals , Non-ionic binder 0.5 to 30% by weight, a mixture consisting of 0 to 30% by weight of the flexible component / binding component to prepare a slurry by producing a slurry, characterized in that the method of producing a non-ionic absorber characterized in that the spray drying process It is about.

Description

Manufacturing method of nonionic absorbent and manufacturing method of fabric softener-containing detergent using same

The present invention relates to a method for producing a nonionic absorbent and a method for producing a fabric softener-containing detergent using the same. More specifically, the present invention provides a fabric softener-containing detergent having excellent physical properties of the final particles by preparing a nonionic absorbent which absorbs the nonionic surfactant as a cleaning component in the preparation of the fabric softener-containing detergent having a nonionic surfactant as a main component. A nonionic absorbent and a fabric softener-containing detergent for preparing.

In general, the softening method of the garment is to obtain a softening effect by the addition of a liquid or powdered fiber softener in the last rinsing process of the garment washing process or a fabric softener formulated in a non-woven fabric, sheet, etc. in the clothes dryer. Method and the like. In particular, low temperature washing and natural drying method is mainly made of a liquid softener in the rinsing step. However, the liquid type softener has the advantages of excellent flexibility and good fragrance, but it is inconvenient to put it in the last rinsing, and when used simultaneously with the detergent, cationic surfactant or zwitterionic surfactant and detergent Due to the interaction with the anionic surfactants, there is a disadvantage in that both the cleaning power and the softening effect are significantly reduced.

Therefore, research has been conducted on the fabric softener-containing detergent without such inconvenience. Such prior arts include USP3862058, USP4062647, USP4472287, GB2160886, EP0011340, GB2206902, EP0376398, USP4659496, and the like. To give the softening effect by using a special type of silicone oil, etc., which has a softening effect, or to package the non-woven fabric with a detergent and a soft component that does not dissolve at low temperature, and after the washing is finished, put the clothes into the clothes dryer and dry the clothes dryer. It is a technology related to a special type of fabric softener-containing detergent designed to absorb water insoluble cationic surfactant or zwitterionic surfactant, which is a flexible component, and to exhibit a softening effect.

The fabric softener-containing detergents described above form bentonite-cationic surfactant conjugates using bentonite with ion-exchange ability to reduce the formation of conjugates between anionic surfactants and cationic or zwitterionic surfactants, thereby minimizing the detergency and softening effect. It has the characteristic to However, it is impossible to fundamentally prevent the mutual adverse effects between the anionic surfactant and the cationic and zwitterionic surfactant in the cleaning solution, and the effective content of the insoluble bentonite is 10% by weight or more, which increases the price and contaminates when adsorbed onto clothing. There is a problem. In addition, most of the cationic and zwitterionic surfactants exhibit poor solubility and dispersibility at low temperatures, and thus exhibit flexibility in high temperature washing and clothes dryers. However, washing and flexibility in washing conditions of low temperature washing and natural drying are difficult. In addition, the silicone oil having a softening effect is less than the cationic surfactant or zwitterionic surfactant in the effect and has the disadvantage that the price is also expensive.

As a technique for preventing the formation of the conjugate of the cation-anionic surfactant, there are Korean Patent Application Nos. 94-37950, 94-38911, 94-15805, and the like. The above technique uses a cation using a nonionic surfactant as a cleaning component. -It is a technology to make the fiber softening effect by preventing the formation of the binder of the anionic surfactant. However, the detergents produced by these technologies have a relatively high specific gravity, which makes it difficult to manufacture a detergent with a low apparent specific gravity of 0.6 g / cc or less, and causes a leakage of nonionic surfactants for long-term storage. have.

As a result of our intensive efforts to solve the above problems, the researchers have improved the physical properties by stably impregnating the nonionic surfactant as a liquid component using a nonionic absorbent absorbing the nonionic surfactant, thereby improving the uniformity and long-term stability of the particle size. It has been found that by improving the stabilization of the nonionic surfactant, it is possible to eliminate leakage during long-term storage and to facilitate specific gravity control.

The present invention is 30 to 80% by weight of one or more mixtures selected from the group consisting of sodium carbonate (Na ₂ CO ₃ ), sodium bicarbonate (NaHCO ₃ ) and sodium sulfate (Na ₂ SO ₄ ), 0 to 40% by weight of water-insoluble minerals , Non-ionic binder 0.5 to 30% by weight, a mixture consisting of 0 to 30% by weight of the flexible component / binding component to prepare a slurry by producing a slurry, characterized in that the method of producing a non-ionic absorber characterized in that the spray drying process It is about.

In the present invention, the non-ion absorber prepared as described above is spray-dried non-ion absorber into a high-speed rotary granulator and absorbed in the alkyl ethoxylate and alkyl polyglucoside as a liquid cleaning component, and then the It is related with the manufacturing method of the fabric softener containing detergent characterized by mixing, grind | pulverizing, granulating, apply | coating a water-insoluble inorganic substance to the surface of a particle | grain, and mixing an additive.

Hereinafter, the present invention will be described in more detail. 30 to 80% by weight of one or more mixtures selected from the group consisting of sodium carbonate (Na ₂ CO ₃ ), sodium bicarbonate (NaHCO ₃ ) and sodium sulfate (Na ₂ SO ₄ ), 0 to 40% by weight of water-insoluble inorganics, nonionic A mixture consisting of 0.5 to 30 wt% of the binder and 0 to 30 wt% of the flexible / binding component is mixed with water to prepare a slurry, and then a nonionic absorbent is prepared through a countercurrent spray drying process. The prepared nonionic absorber is placed in a high speed mixer having a vertical or horizontal stirring shaft (High Speed Mixer, Lodige Mixer, or Schugi Mixer), and a nonionic surfactant, which is a liquid cleaning component, is added to the mixer and absorbed by the nonionic absorber. And a flexible component are mixed to pulverize, granulate, apply a surface modifier to the surface of the particles, and mix the additive to prepare a fabric softener-containing detergent.

The nonionic absorbent according to the present invention absorbs nonionic surfactants, which are liquid cleaning components, and stabilizes them in detergent particles to prevent leakage of liquid raw materials, maintain particle properties in good condition, and facilitate the control of the apparent specific gravity of the detergent. Therefore, the anionic organics should not be used to prevent the formation of a binder with a flexible cationic and zwitterionic surfactant. As the alkali and filler of the nonionic absorber, one or more mixtures selected from the group consisting of sodium carbonate (Na ₂ CO ₃ ), sodium bicarbonate (NaHCO ₃ ) and sodium sulfate (Na ₂ SO ₄ ) are used. It is suitable to use 30 to 80% by weight of such alkali and filler. When used at less than 30% by weight, the relatively high cost of water-insoluble inorganic substances, nonionic binders, flexible / binding components have a disadvantage in that the raw material cost increases, the content of the other raw material is increased, the strength of the nonionic absorber particles It becomes excessively strong and the particle surface becomes thick, and it becomes difficult to absorb the nonionic surfactant which is a washing | cleaning component. In addition, when used by more than 80% by weight, the crystal structure of the inorganic sodium carbonate, sodium bicarbonate, sodium sulfate is excessively increased, so that the absorbency of the liquid component of the absorber particles is reduced.

In water-insoluble inorganic substances, the liquid component absorbed in the nonionic absorber serves to stabilize the nonionic surfactant. The water-insoluble inorganic substance uses one or more selected from zeolite, bentonite, talc, clay and fine powder silica. The water-insoluble inorganic material may be used in an amount of 0 to 40% by weight, but the smaller the amount used, the higher the specific gravity of the non-ionic absorber is, thereby increasing the apparent specific gravity of the finished product. However, as the binding force of the absorber particles is lowered, the particles are destroyed during the manufacturing process, so that the fine powder is increased, resulting in deterioration of the appearance and powder properties of the product. The nonionic binder has an effect of improving the particle appearance of the product and the powder properties such as fluidity by enhancing the binding force of the nonionic absorber particles. Nonionic binders use one or more selected from polyethylene glycol, polypropylene glycol and alkyl ethoxylates. In this case, polyethylene glycol and polypropylene glycol are usually those having a molecular weight of 1000 to 25000 used in the manufacture of powder detergent, and in the case of alkyl ethoxylate, an appropriate number of moles of ethylene oxide added is 12 to 40, but the number of moles of addition is low. If the alkyl ethoxylate is present in the liquid phase does not exhibit a binding force and the number of moles of ethylene oxide added more than 40 has the disadvantage of excessively strong strength and hinder the absorption of the liquid nonionic surfactant. In the present invention, it is preferable to use about 0.5 to 30% by weight of the nonionic binder. If the content of the nonionic binder is 0.5% by weight or less, it is difficult to show the binding force. If the content of the nonionic binder is 30% by weight or more, the binding force is excessively increased, thereby increasing the strength of the particles and preventing the absorption of the liquid nonionic surfactant.

Examples of the flexible / bonding component include quaternary ammonium salts having an alkyl group of formula (1), quaternary ammonium salts having an alkyl ester of formula (2), and imidazoline cationic surfactant of formula (3). When used, they are adsorbed on the surface of the fiber during washing to show the softening effect and the antistatic effect as well as to strengthen the binding force of the nonionic absorbent.

Formula 1

Formula 2

Formula 3

In the above formula,

R ₁ and R ₂ are an alkyl group or alkenyl group having 10 to 28 carbon atoms,

X is Cl or CH ₃ OSO ₃ .

In addition, due to its softening and antistatic effects, cationic surfactants, which are flexible and binding components, are difficult to powder their properties when a large amount of particles of fiber softener-containing detergents or particles of powder detergent are added to processes and additives. There is also an effect that the stick (stick) is bad product properties. Therefore, it is often advantageous to add the nonionic absorber to the physical properties of the product.

However, when the property of the flexible component is a powder or a small amount of liquid raw material, it does not matter much. When applied to more than 30% by weight of the non-ionic absorbent because of the slippery nature of the flexible component surface of the particles is very slippery, rather it interferes with the binding of the detergent particles. The nonionic absorbent is prepared by preparing a water-soluble slurry having a solid content of 10 to 70% by weight with the above-mentioned composition, and then drying the slurry by using a conventional counter-current spray dryer used for preparing a detergent. Here, the solid content is the weight% of the solid material of the slurry, but if the solid content is less than 10%, the moisture content and efficiency of the drying apparatus decreases because the moisture content is too high. If the weight is more than 70% by weight, the slurry viscosity is so high that it is difficult to transfer the slurry.

The apparent density of the nonionic absorber obtained in the present invention is 0.3 to 0.7 g / cm 3.

20 to 80% by weight of the nonionic absorber prepared by the above method, the stirring blades of one or more than 15 to 30% by weight of the alkyl ethoxylate and the alkyl polyglucoside as the liquid cleaning components on the vertical stirring shaft High Speed Mixer (Fukae Powtec, Japan, Schugi Mixer; Schugi, Germany) equipped with single or more grinders on separate shafts or horizontal stirring shaft It is impregnated and granulated by spraying in a high speed rotary granulator (Lodige Mixer, Lodige, Germany) equipped with one or more grinders on the shaft, stirring and grinding.

In this case, one or one selected from sodium carbonate (Na ₂ CO ₃ ), sodium bicarbonate (NaHCO ₃ ), potassium carbonate (K ₂ CO ₃ ), potassium hydrogen carbonate (KHCO ₃ ), and sodium sulfate (Na ₂ SO ₄ ). 0 to 40% by weight or more of alkali builders may be used simultaneously. Alkali builders increase the concentration of hydrogen ions in the washing solution during washing, making it easy to remove contaminants attached to the fibers, as well as absorbing liquid raw materials. When more than 40% by weight is used, the amount of the mixed powder that is relatively pretreated becomes small, so that the absorption power of the liquid raw material is weakened, so that the particles are sticky.

The alkali builder and a powdered or liquid cationic and amphoteric surfactant are added simultaneously to the process. In this process, as the stirring and pulverization proceeds, the surface of the particles gradually thickens as the particles absorb a large amount of liquid components. At this time, the surface of the particles prepared by using one or more surface modifiers selected from zeolite, bentonite, talc, clay, fine powder silica and the like is subjected to surface modification of the detergent particles. In addition, additives such as flavors, enzymes, antifoaming agents, anti-adhesion agents, fluorescent dyes, and fiber dye inhibitors may be used as necessary.

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

Comparative Example 1

A detergent containing a detergent composition having the ingredients and contents shown in Table 1 was sprayed downward from the top of the countercurrent spray drying apparatus to prepare a powdery powder detergent.

Table 1.

1) Tinopal CBS-X (Ciba-Geigy, Switzerland)

2) Savinase 12.0T (Novo Nordisk, Denmark)

3) LDC1215 (DC Silicon, Korea)

4) NH15073 (US IFF company)

Examples 1-6

The mixed powder having the components shown in Table 2 below was dried using a countercurrent spray dryer to prepare the nonionic absorbents of Examples 1 to 6.

Table 2.

1) Average molecular weight 10000

2) Average molecular weight 10000

3) Cationic surfactant of formula (1), distearyl ammonium chloride (Aerosurf TA-100, Witco, USA)

4) Cationic Surfactant of Formula (2), Ditlowcarboxyethylhydroxyethylmethylammoniummethosulfate (Rewoquat WE18, Witco, USA)

5) Zwitterionic surfactant of general formula (3), methyltallowamidoethyltallowimidazoliniummethylsulfate (Varisoft 475, Witco, USA)

Examples 7-16

Examples 1, 3 and 5 were prepared in Examples 7 to 16 using the composition and the high-speed rotary assembly of Table 3 below.

Table 3.

1) 12-14 carbon atoms and 7 mol of average added moles of ethylene oxide

2) Carbon number 12-14 of an alkyl group, 1.5 mol of glucoside average added moles

3) Cationic surfactant of formula (1), distearyl ammonium chloride (Aerosurf TA-100, Witco, USA)

4) Cationic Surfactant of Formula (2), Ditlowcarboxyethylhydroxyethylmethylammoniummethosulfate (Rewoquat WE18, Witco, USA)

5) Tinopal CBS-X (Shiba, Gaiza)

6) Savinase 12.0T (Denovo, Novo Nordisk)

7) NH15073 (IFF, USA)

8) HS; High Speed Mixer, Fukae Powtec, Japan.

SC; Schugi Mixer, Schugi, Germany

LO; Lodige Mixer, Lodoge, Germany

Experimental Example

The nonionic absorbents and the fabric softener-containing detergents prepared in Examples 1 to 16 were tested under the following conditions.

(1) cleaning power

The fabric softener-containing detergent prepared in Examples 7 to 16 was subjected to a washing force test under the following conditions, and is shown in Table 4 below.

Washing Machine: Terg-O-Tometer

Washing temperature: 20 ℃

Number of washes: hardness 40ppm Ca ⁺⁺ , 10ppm Mg ⁺⁺

Bath ratio: 4.5g contaminated cloth / 1ℓ

Pollution Gun: EMPA Art No.101 (Olive Oil, Carbon Black / Cotton)

Detergent Concentration: 0.67g / ℓ

Evaluation: The cleaning power was converted to Comparative Example 1 as 100.

(2) apparent specific gravity

The apparent specific gravity of the nonionic absorbent and the fabric softener-containing detergent prepared from Examples 7 to 16 was measured using an apparent specific gravity measuring device (Powder Tester; Hosogawa Micron, Japan), and is shown in Table 4 below.

(3) liquidity

100 ml of the nonionic absorbent and the fabric softener-containing detergent prepared from Examples 7 to 16 were measured to pass through a funnel having a lower diameter of 10 mm and are shown in Table 4 below.

(4) solubility

10 g of the nonionic absorbent and the fabric softener-containing detergent prepared in Examples 7 to 16 were placed in 1 L of ion-exchanged water and stirred for 5 minutes to measure the dry weight% of the residue remaining after passing the detergent solution through a 200-mesh superstructure. It is shown in Table 4 below.

(5) yield

The yields of the nonionic absorbents and the fabric softener-containing detergents prepared in Examples 7 to 16 were measured and shown in Table 4 below.

(6) fiber softening effect

The fabric softening effect of the fabric softener-containing detergents prepared in Examples 7 to 16 was shown in Table 4 below under the following conditions.

Washing Machine: Waist Type Automatic Washing Machine

Washing temperature: 20 ℃

Number of washes: hardness 40ppm Ca ⁺⁺ , 10ppm Mg ⁺⁺

Bath ratio: 200g terry towels / 30ℓ washing water

Test gun: terry towel

Detergent Concentration: 0.67g / ℓ

Evaluation: To give a soft touch to each towel by the touch of 30 panelists selected, the score was selected from 1 to 5 points and the average value is shown in Table 4.

(7) antistatic effect

The antistatic effect of the fabric softener-containing detergent prepared from Examples 7 to 16 is shown in Table 4 below.

Detergent Concentration: 0.67g / ℓ

Temperature: 23 ± 1 ℃

Relative Humidity: 45 ± 1%

Method: Perform antistatic test by KS-K-0555 B method

(8) long-term stability

Take 1 kg of each of the fabric softener-containing detergents of Examples 7 to 16 into a 2 kg paper carton and store it for 2 weeks with the lid open at a temperature of 40 ° C. and a relative concentration of 80% R ^H. The degree of penetration of the nonionic surfactant was measured visually.

The experimental results are shown in Table 4 below.

Table 4.

As shown in Table 4, the fabric softener-containing detergent of the present invention can be seen that the apparent density is varied, fluidity, solubility, yield, washing power, long-term storage stability and excellent flexibility and antistatic properties.

Claims (7)

30 to 80% by weight of one or two or more mixtures selected from the group consisting of sodium carbonate (Na ₂ CO ₃ ), sodium bicarbonate (NaHCO ₃ ) and sodium sulfate (Na ₂ SO ₄ ), 0 to 40% by weight of water-insoluble inorganics, nonionic A slurry consisting of 0.5-30 wt% of the binder and 0-30 wt% of the flexible / binding component is mixed with water to prepare a slurry, followed by a countercurrent spray drying process, wherein the flexible / binding component is represented by Formula (1). A quaternary ammonium salt system having an alkyl group added, a quaternary ammonium salt system having an alkyl ester of formula (2) added or an imidazoline cationic surfactant of formula (3) having a specific gravity of 0.3-0.7 g / cm 3 Method for producing an ion absorber. Formula 1 Formula 2 Formula 3 In the above formula, R ₁ and R ₂ are an alkyl group or alkenyl group having 10 to 28 carbon atoms, X is Cl or CH ₃ OSO ₃ . The method for producing a nonionic absorber according to claim 1, wherein the water-insoluble inorganic substance is one kind or two or more kinds selected from zeolite, bentonite, talc, clay and fine powder silica. The method of claim 1, wherein the nonionic binder is one or two or more selected from polyethylene glycol, polypropylene glycol and alkyl ethoxylates having an added mole number of 12 to 40. The nonionic absorbent prepared by the method of claim 1 is spray-dried into the high-speed rotary granulator, and then absorbed in the alkyl ethoxylate and the alkylpolyglucoside as a liquid cleaning component, and then mixed with an alkali builder and a flexible component. A method for producing a fabric softener-containing detergent, characterized in that granulation is carried out after pulverization, and a water-insoluble inorganic substance is applied to the surface of the particles and an additive is mixed. The method of manufacturing a fabric softener-containing detergent according to claim 4, wherein the amount of the nonionic absorbent is 20 to 80% by weight. 5. The high speed rotary granulator according to claim 4, wherein the high speed rotary granulator is equipped with a stirring blade on a vertical stirring shaft, a single or more grinding device is mounted on a separate shaft, or a stirring shaft is mounted on a horizontal stirring shaft, and is a separate shaft. Method for producing a fabric softener-containing detergent, characterized in that the single or more grinding device is attached to. The method for producing a fabric softener-containing detergent according to claim 4, wherein the alkali builder is one or more selected from sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate and sodium sulfate.