JP2001123198A - Surfactant composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surfactant composition having low viscosity easily handleable at production temperature and having characteristics suppressing oozing out of a nonionic surfactant and curable so as to improve strength of a detergent composition at storage temperature and excellent in deterging property and a method for efficiently producing the composition and provided a powdery detergent composition including the above composition and a method for producing the powdery detergent composition. SOLUTION: This surfactant composition comprises (a) 100 pts.wt. nonionic surfactant having <=30% melting point, (b) 10-300 pts. wt. anionic surfactant having sulfate/ sulfonate group, (c) 1-100 pts.wt. solidifying agent for the component (a) which is one or more kinds of compounds selected from (c-1) an anionic surfactant not having sulfate/sulfonate group though the component c has carboxy/phosphoate group and (c-2) a compound having >=35% melting point and having compatibility with the component (a) and (d) 1-100 pts.wt. polymer having carboxy group. The surfactant composition has a temperature area in which the viscosity is <=10 Pa.s at a temperature of pour point or above of the composition and has a temperature area in which approach hardness of the composition becomes >= 100 g/cm2 in a temperature range lower than the pour point and higher than the melting point of the component (a).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surfactant composition containing a nonionic surfactant and a method for producing the same, and a powder detergent composition containing the surfactant composition and a method for producing the same.

[0002]

2. Description of the Related Art A nonionic surfactant having a melting point of 30 ° C. or less is excellent in cleaning performance of sebum stains. However, since the nonionic surfactant is liquid or paste at room temperature, it is difficult to mix it with non-liquid detergents such as powder detergents.

Japanese Patent Application Laid-Open No. 5-112797 discloses a method for producing a liquid surfactant composition containing a nonionic surfactant, and this composition is supported on powder to obtain a powder detergent. In such a case, there is a problem in the spotting property and caking property of the nonionic surfactant.

[0004] Japanese Patent Publication No. Hei 8-509775 discloses a premix in which a structuring agent containing a polymer is dissolved in a nonionic surfactant, but is added as a structuring agent. The polymer is a polymer having two or more hydroxyl functional groups, and is used to improve the physical properties of the premix.
0% by weight or more is added, which is extremely disadvantageous in terms of detergency.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a powder detergent composition which has a sufficiently low viscosity that it can be easily handled in a temperature range during production (preferably 90 ° C. or lower), On the other hand, in the temperature range at the time of storage of the detergent composition, the detergent composition also has the property of suppressing stains of the nonionic surfactant and curing for the purpose of improving the strength of the detergent composition. An object of the present invention is to provide a surfactant composition, a method for efficiently producing the surfactant composition, a powder detergent composition containing the surfactant composition, and a method for producing the same.

[0006]

That is, the gist of the present invention is as follows.
[1] Nonionic surfactant having a melting point of 30 ° C. or lower (component (a)), anionic surfactant having a sulfate group or a sulfonic acid group (component (b)), immobilization of component (a) An agent (component (c)) and a polymer having a carboxyl group (component (d)), wherein the component (c) has a carboxyl group or a phosphate group but does not have a sulfate group or a sulfonic acid group. Anionic surfactant (component (c-1))
And a surfactant composition having at least one compound selected from the group consisting of compounds having a melting point of 35 ° C. or higher (component (c-2)) compatible with component (a), wherein component (a) 100
The content of the component (b) is 10 to 300 parts by weight, the content of the component (c) is 1 to 100 parts by weight, the content of the component (d) is 1 to 100 parts by weight, and At a temperature above the pour point of the surfactant composition, the viscosity of the composition is 10P
a.s or less, and in a temperature range lower than the pour point of the composition and higher than the melting point of the component (a), the composition has a temperature range where the penetration hardness of the composition is 100 g / cm ² or more. A surfactant composition, [2] a method for producing the surfactant composition according to the above [1], wherein a component (a) is present;
(B) a method for producing a surfactant composition, comprising a step of neutralizing the acid precursor of the component with a liquid alkali compound using a loop reactor, [3] the surfactant composition 1 according to [1];
A powder detergent composition comprising 100 to 2000 parts by weight of a powdery substance with respect to 00 parts by weight, and [4] the surfactant composition according to [1], wherein the viscosity of the surfactant composition is The present invention relates to a method for producing a powder detergent composition including a step of mixing with a powdery substance at a temperature of 10 Pa · s or less.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The nonionic surfactant (a) has a melting point of 30 ° C. or less, preferably 25 ° C.
The temperature is particularly preferably 22 ° C. or less. For example, polyoxyalkylene alkyl (phenyl) ether, alkylene polyglycoside, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene glycol fatty acid ester, polyoxyethylene polyoxypropylene block polymer, and polyoxyalkylene alkylol (fatty acid) amide are preferable. As an example. Among them, a polyoxyalkylene alkyl ether obtained by adding 4 to 12 mol (preferably 6 to 10 mol) of an alkylene oxide to an alcohol having 10 to 14 carbon atoms is particularly preferable. Here, as the alkylene oxide,
Examples include ethylene oxide and propylene oxide, and preferably ethylene oxide. As the component (a), one or more types can be used. The component (a) may be blended as an aqueous solution. Although the content of the component (a) in the surfactant composition is not particularly limited, for example, 15 to 85% by weight
, And more preferably 25 to 70% by weight. The content is preferably 15% by weight or more from the viewpoint of cleaning performance, and is preferably 85% by weight or less from the viewpoint of handling various types of stains.

[0008] The anionic surfactant having a sulfate group or a sulfonic acid group of the component (b) can obtain desired foaming property and cleaning performance by being used in combination with the nonionic surfactant of the component (a). Can be.

The component (b) includes a sulfate ester of an alcohol having 10 to 18 carbon atoms, a sulfate ester of an ethoxylated product of an alcohol having 8 to 20 carbon atoms,
Preferred examples include 0 to 18 alkylbenzene sulfonates, paraffin sulfonates, α-olefin sulfonates, α-sulfofatty acid salts, and α-sulfofatty acid alkyl ester salts. Among them, linear alkylbenzene sulfonates having 12 to 14 carbon atoms in the alkyl chain are more preferable, and alkali metal salts such as sodium and potassium, and amine salts such as monoethanolamine and diethanolamine are particularly preferable. These (b) components are preferably mixed in the form of an acid precursor and neutralized. Further, as the component (b), one or more kinds can be used.

The content of the component (b) is 10 to 300 parts by weight, preferably 20 to 100 parts by weight of the component (a).
The amount is from 200 to 200 parts by weight, more preferably from 30 to 180 parts by weight. The content is 1 from the viewpoint of foaming property and cleaning performance.
0 parts by weight or more, and from the viewpoint of handleability, 300 parts by weight or less.

The component (c) is a fixing agent for the component (a). In the present invention, the immobilizing agent refers to normal temperature, for example, 25
It means a base capable of suppressing the fluidity of a nonionic surfactant liquid at a temperature of ° C. and increasing the hardness of the composition containing the nonionic surfactant in a state where the fluidity is lost. For example, as shown in FIG. 1, a mixture (composition (X)) of the component (a), the component (b), and the component (d) has a small increase in the penetration hardness due to a decrease in temperature. On the other hand, the composition (X)
The composition (Y) obtained by adding the component (c) to the mixture has a low penetration hardness at the pour point (T ₂ ) of the composition, but rapidly increases at a temperature higher than the melting point (T ₁ ) of the component (a). In addition, the composition has a property that the penetration hardness of the composition increases. The penetration hardness was measured using a rheometer (“NRM-
3002D type) and a circular adapter (“No. 3”, 8φ) having a diameter of 8 mm and a bottom area of 0.5 cm ² , and the adapter enters the inside of the surfactant composition at a speed of 20 mm / m.
It can be obtained as a value obtained by dividing the load at the time of entering 20 mm in by the bottom area of the adapter.

The component (c) is at least one selected from the group consisting of the components (c-1) and (c-2) shown below.

The component (c-1) is an anionic surfactant having a carboxyl group or a phosphate group but not having a sulfate group or a sulfonic acid group. Specific examples include one or more anionic surfactants selected from the group consisting of fatty acid salts, hydroxy fatty acid salts, and alkyl phosphates. Among them, one or more selected from sodium salts of potassium or alkali metal salts of potassium fatty acids or amine salts such as alkanolamines and the like are preferred in terms of solubility. Particularly preferably, the number of carbon atoms is 1 in terms of suppression of spotting and strength of detergent particles.
It is at least one selected from sodium and potassium salts of 4 to 20 saturated fatty acids. Fatty acid salts are preferred because they exhibit a buffering effect on neutralization and can stably neutralize the acid precursor of component (b). It is preferable that these components (c-1) are blended into the surfactant composition in the form of an acid precursor and neutralized.

The component (c-2) is a compound having a melting point of 35 ° C. or higher, which is compatible with the component (a). One or more selected from the group consisting of a polyoxyalkylene type nonionic compound having a weight average molecular weight of 3,000 to 30,000, a polyether nonionic compound having a weight average molecular weight of 3,000 to 30,000, and the like. Particularly preferred are polyethylene glycol, polypropylene glycol and polyoxyethylene alkyl ether, and among them, polyethylene glycol having a weight average molecular weight of 3,000 to 30,000 (preferably 5,000 to 15,000) is preferred. Here, the compatibility refers to a property that the mixture of the component (a) and the component (c-2) mixes well at a temperature equal to or higher than the pour point of the mixture and is hardly phase-separated.

In the present invention, the component (c-1) alone or the component (c-2) may be blended, or both the component (c-1) and the component (c-2) may be blended. You may. When both are used in combination, the effect of preventing spots and the anti-caking property can be further improved, so that it is more preferable. In this case, the weight ratio of the component (c-1) to the component (c-2) is preferably 10/1 to 1/10, and 8/1.
／ To よ り is more preferable, and 5/1 to ５ is particularly preferable.

The content of the component (c) is 1 to 100 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the component (a). The content is 1 part by weight or more from the viewpoint of preventing stains of the nonionic surfactant when the surfactant is incorporated into the non-liquid detergent composition, and the handleability of the surfactant composition is From the viewpoint, it is 100 parts by weight or less.

The polymer having a carboxyl group as the component (d) has a function of sequestering metal ions, an effect of dispersing solid particle stains from clothes into a washing bath, and a function of reattaching the particles to clothes (recontamination). Therefore, the surfactant composition containing the component (d) can provide high cleaning performance. Furthermore, since the component (d) also has a buffering effect on pH, it has the effect of increasing the pH stability of the surfactant composition, increasing the storage stability, and increasing the stability during production.

The component (d) has a molecular weight of 1,000 to 10
Homopolymers and / or copolymers of acrylic acid are preferred. In particular, polyacrylic acid salts having a molecular weight of 1 1,000 to 80,000 and / or acrylic acid - maleic acid copolymer salts (Na, K, NH ₄ and the like) is preferable. The salt of the polymer may be neutralized after being added in acid form. One or more of these components (d) can be used.

The content of the component (d) is 100% for the component (a).
1 to 100 parts by weight, preferably 2 to 100 parts by weight
80 parts by weight, more preferably 5 to 50 parts by weight. The content is 1 part by weight or more from the viewpoint of cleaning performance,
From the viewpoint of the freedom of blending, the content is 100 parts by weight or less.

It is preferable that the surfactant composition of the present invention has an excess alkali. The excess alkalinity is preferably 0.5 to 20 mol%, more preferably 1 to 10 mol%, and particularly preferably 2 to 5 mol%. Within this range, the storage stability and hue of the composition are further improved, which is preferable. The excess alkalinity is defined as a percentage of the molar amount of the alkali compound contained in excess with respect to the molar amount of the component (c-1) when the component (b) and the component (c-1) are present. .

Further, the surfactant composition of the present invention may contain water. Particularly, the composition is (c-1)
When a component is contained, it is preferable that water is further contained. Among them, when a fatty acid salt is used as the component (c-1), when water is added, the compatibility with the component (a) increases, and there is also a viscosity reducing effect at a temperature equal to or higher than the pour point of the composition,
Further, it is preferable from the viewpoint of handling in production. The content of water is preferably 5 to 25% by weight of the surfactant composition, more preferably 5 to 20% by weight, more preferably 9% by weight.
-15% by weight, more preferably 10-14% by weight, particularly preferably 10-13% by weight, most preferably 10.5% by weight.
１12.5% by weight. The content can also be adjusted by adding water to the surfactant composition or adjusting the water content of the raw material components.

Further, the surfactant composition of the present invention comprises:
Known components commonly used in detergents, for example, surfactants known in the field of detergents for clothing; anti-redeposition agents such as carboxymethylcellulose; reducing agents such as sulfites; and fluorescent whitening agents are appropriately contained. May be.

The surfactant composition of the present invention having the above composition has a pour point equal to or higher than the pour point of the surfactant composition from the viewpoint of handleability during the production of the composition and the detergent composition using the composition. It has a temperature range in which the viscosity of the composition at a temperature is 10 Pa · s or less, preferably 5 Pa · s or less, particularly preferably 2 Pa · s or less. The temperature range is preferably 90 ° C. or lower, more preferably 80 ° C. or lower, particularly preferably 70 ° C. or lower, from the viewpoint of the stability of the surfactant composition. Here, the viscosity is measured using a B-type viscometer (TOKY
OKEIKI “DVM-B type”), rotor No.
3. Measured under the condition of a rotation speed of 60 r / min.
If the measured value under these conditions exceeds 2 Pa · s and measurement becomes impossible, the rotor No. 3. Rotational speed 12r / mi
The viscosity is determined by measuring under the conditions of n.

In addition, the surfactant composition of the present invention can prevent the nonionic surfactant from bleeding during storage of the detergent composition using the composition. The composition has a temperature range where the penetration hardness of the composition is 100 g / cm ² or more, preferably 300 g / cm ² or more, particularly preferably 800 g / cm ² or more in a temperature range lower than the melting point of the component (a). The pour point can be measured by the method of JIS K 2269. The melting point was measured using the “Mettler FP81” (Mettler Instrument) of the FP800 Thermo System.
e AG) at a heating rate of 0.2 ° C./min.

In the present invention, the surfactant composition having such a penetration hardness suppresses stains of the nonionic surfactant within the temperature range during storage of the detergent composition using the surfactant composition. In addition, it has excellent properties of curing and improving the strength of the detergent composition.

As a method for producing a surfactant composition having such a constitution, the acid precursor of the component (b) is neutralized with a liquid alkali compound using a loop reactor in the presence of the component (a). And a method having a step. In the present invention, by using a loop reactor, not only improvement of production efficiency due to the possibility of continuous reaction,
The heat of neutralization generated when the acid precursor of the component (b) is neutralized can be efficiently removed, so that a high-quality surfactant composition is obtained.

Regarding the component (b) and the component (c-1),
The acid precursor may be supplied to the loop reactor simultaneously with the nonionic surfactant and neutralized with a liquid alkali compound to prepare the acid precursor, or one or both of the acid precursors may be nonionic surfactant. After mixing with the activator, the mixture may be supplied to a loop reactor and neutralized with a liquid alkali compound to prepare the mixture. Here, the compounding amount of the acid precursor of the component (b) is as follows:
The amount is such that the amount of the component (b) generated by neutralization is 10 to 300 parts by weight with respect to 100 parts by weight of the component (a). The amount of the acid precursor of the component (c-1) is as follows:
This amount is 1 to 100 parts by weight as the amount of the component (c-1) generated by neutralization with respect to 100 parts by weight of the component (a).

As the liquid alkali compound used for neutralizing the acid precursor of the component (b), an alkali metal hydroxide aqueous solution having a hydroxide concentration of 60% by weight or less is preferable from the viewpoint of handleability. Those having a substance concentration of 30 to 55% by weight are more preferable. As the alkali metal hydroxide, sodium hydroxide and potassium hydroxide are preferable. Further, two or more kinds of alkali compounds may be used. In this case, the content of the liquid alkali compound may be at least the amount necessary for neutralizing the acid precursor of the component (b).

The liquid alkali compound used for neutralizing the acid precursor of the component (c-1) can be used without limitation as long as it is an alkali compound that can be used for neutralizing the acid precursor of the component (b). And (b) may be the same as or different from those used for neutralizing the acid precursor. In this case, the content of the liquid alkali compound may be at least the amount necessary for neutralizing the acid precursor of the component (c-1).

The component (d) may be added as it is, or may be added in an acid form and neutralized with a liquid alkali compound. When added in the acid form, the liquid alkali compound used for neutralization can be used without limitation as long as it is an alkali compound that can be used for neutralizing the acid precursor of the component (b). It may be the same as that used for neutralization of the precursor, or may be different. In this case, the content of the liquid alkali compound may be at least the amount necessary for neutralizing the acid form component (d).

In order to neutralize in the presence of the component (a), for example, after the inside of the loop is first filled with the component (a), another raw material component may be supplied into the loop.

In a preferred embodiment of the method for supplying the raw material components to the loop reactor, the component (a), the acid precursor of the component (b), the liquid alkali compound, the component (c) and the component (d) are each used. In this embodiment, the fuel is separately supplied to the loop reactor. When the acid precursor of the component (c-1) is blended as the component (c), the acid precursor of the component (b) is neutralized with a liquid alkali compound from the viewpoint of easy handling in production.
An embodiment in which the acid precursor of the component (c-1) is added for neutralization is particularly preferred. For example, it is preferable to add the acid precursor of the component (c-1) to the mixture discharged from the loop reactor. Specifically, it is advantageous that a heat exchanger is installed in the loop reactor for the purpose of removing the heat of neutralization, since scale formation on the heat transfer surface is prevented. The liquid alkali compound necessary for neutralizing the acid precursor of the component (c-1) may be supplied in advance in a loop reactor, or supplied in the middle of a discharge line from the loop reactor. May be.
When a mixing tank is installed following the discharge line from the loop reactor, it may be added in the mixing tank. When a liquid alkali compound is supplied in the mixing tank, the amount of the acid precursor of the component (c-1) which is not neutralized is 10% of the surfactant composition in view of the stability of the surfactant composition. % By weight, preferably 5% by weight or less, particularly preferably 3% by weight or less.

As the loop reactor, a general loop reactor for neutralization can be used. Essentially a closed loop type is preferred. The loop reactor usually includes a mixing device and a circulation device. A heat exchange device is provided downstream of the mixing device as needed, and a supply port for each component is provided upstream of the mixing device. An outlet for discharging the mixture is provided upstream of the supply port. A part of the mixture is discharged from the loop through the outlet, and the rest of the mixture is recirculated in the loop.
At this time, from the viewpoint of efficiently removing the generated heat of neutralization and productivity, the circulation magnification is preferably 3 to 20 times, and
5 times is more preferable. The circulation magnification is defined as a value obtained by dividing the flow rate of the liquid circulating in the loop by the total supply flow rate of each raw material supplied to the loop. The loop reactor is preferably kept warm by a jacket. As the mixing device, an in-line mixer or a centrifugal pump can be used. A mixing tank may be provided following the discharge line from the loop reactor.

Further, a detergent composition can be produced by mixing the thus obtained surfactant composition with another powdery substance. In addition, as a powdery substance, for example, a builder such as zeolite, sodium carbonate, and crystalline silicate which is generally used for a detergent for clothing is mentioned, and one or more builders and / or a builder which is generally used for a detergent composition are used. Base granules obtained by drying a slurry appropriately mixed with a base are also included.

Examples of the form of the detergent composition include convertible forms such as paste, dough, powder, and sheets and tablets obtained by processing them. The desired form can be obtained by appropriately changing the mixing ratio of the powdery substance and the powdery substance.

For example, by increasing the amount of the powdery substance with respect to the amount of the surfactant composition, the form of the detergent composition changes from paste to dough or powder.
Generally, 20 to 1000 parts by weight of a powdery substance is blended with 100 parts by weight of the surfactant composition, and 50 to 2,000 parts by weight of a powdery substance is blended with 100 to 2000 parts by weight of a powdery substance. A powdery form can be obtained by blending in parts by weight.

Among them, the most common form of a detergent for clothing is in the form of a powder, and such a powder detergent composition (hereinafter, referred to as a powder detergent composition) is used.
Detergent group), the surfactant composition 1
It is preferable to add 150 to 2000 parts by weight of the powdery substance to 00 parts by weight, and particularly preferably 200 to 1000 parts by weight from the viewpoint of detergency.

A preferred method of producing the detergent particles comprises the following step (A), and may further include step (B) if necessary. Step (A): The viscosity of the surfactant composition is 10 Pa ·
mixing the surfactant composition with the powdered substance at a temperature below s. Step (B): a step of mixing the mixture obtained in step (A) with the fine powder and coating the surface of the powder detergent composition with the fine powder. The step (B) includes the case where the disintegration proceeds simultaneously.

In the case where the base granules are used as the powdery substance in the step (A), the content thereof is preferably 60% by weight or more in the powdery substance in view of the solubility of the detergent particles. It is preferably at least 70% by weight, particularly preferably 8% by weight.
0% by weight or more. However, in the case of a detergent particle group further including a surface coating agent, the calculation is performed excluding the amount of the surface coating agent.

The surface coating agent is added to coat the surface of the detergent particles carrying the surfactant composition. The surface coating agent is a solid powder such as an aluminosilicate, Examples include aqueous solutions and melts of polymers and fatty acids.

The above-mentioned base particles may contain, for example, 20 to 90% by weight, 2 to 30% by weight, based on the solid content of the slurry, of the water-insoluble inorganic substance, the water-soluble polymer and the water-soluble salts. The slurry, which is 5 to 78% by weight, can be obtained by drying. Examples of the drying method include spray drying, freeze drying, thin film drying, vacuum drying, kneading drying, and the like. Among them, spray drying is preferred from the viewpoint of productivity and physical properties of the obtained detergent particles. Further, after drying, pulverization and classification can be performed to obtain a base granule group.

The water-insoluble inorganic substance preferably has an average primary particle diameter of 0.1 to 20 μm.
Those having a thickness of 5 to 10 μm are more preferred. Examples include crystalline aluminosilicates, amorphous aluminosilicates, silicon dioxide, hydrated silicate compounds, perlite, clay compounds such as bentonite, etc., and do not promote the cleaning ability or the generation of undissolved residues of the detergent. For these reasons, a crystalline aluminosilicate is preferred. Preferred as the crystalline aluminosilicate is A-type zeolite (for example, trade name: "Toyobuilder"; manufactured by Tosoh Corporation), which is also preferable in terms of sequestering ability and economy. Here, the value of the oil absorption capacity of the A-type zeolite according to the JIS K 5101 method is 40 to 50 mL /.
Preferably, it is 100 g. In addition, P type (for example, trade name: "Doucil A24", "ZSE064", etc .;
Crosfield; oil absorption capacity 60-150mL / 100
g), X type (for example, trade name: “WessalithXD”; Degu)
(ssa; oil absorption capacity: 80 to 100 mL / 100 g), and the hybrid zeolite described in WO 98/42622 is also a preferred crystalline aluminosilicate.

As the amorphous aluminosilicate, SiO ₂ / Al ₂ O ₃ (molar ratio) is preferably 5.0 or less from the viewpoint of maintaining high solubility (not deteriorating) even after long-term storage. More preferably, it is preferably 4.0 or less, more preferably 3.3 or less.
No. 9899, column 12, line 12 to column 13, line 1; column 17, line 34 to column 19, line 17; among them, a mercury porosimeter (manufactured by Shimadzu Corporation) Pore size measured with SHIMADZU Pore Sizer 9320 ").
Those having a volume of 015 to 0.5 μm of 0 to 0.7 mL / g and a volume of 0.5 to 2 μm of pore size of 0.30 mL / g or more are preferable. These water-insoluble inorganic substances may be composed of a single component, or may be composed of a plurality of components.

The water-soluble polymer is not particularly limited as long as it has the effect of improving the washing performance and / or the particle strength of the base granules. For example, carboxylic acid polymers, cellulose derivatives such as carboxymethyl cellulose, polyglyoxylates, aminocarboxylic acid polymers such as polyaspartate, soluble starch, one or more selected from the group consisting of saccharides and the like are exemplified as preferred ones. Among them, carboxylic acid polymers are more preferable. Among the carboxylic acid polymer, acrylic acid - maleic acid copolymer salts (Na, K, NH _4, etc.) and polyacrylate (Na, K, NH ₄ and the like) are particularly excellent. In particular, those having a molecular weight of 1,000 to 100,000 are preferable, those having a molecular weight of 2,000 to 80,000 are more preferable, and those having a molecular weight of 5,000 to 50,000 are particularly preferable.

Examples of the water-soluble salts include water-soluble inorganic salts such as an alkali metal salt such as a carbonate group, a hydrogen carbonate group, a sulfate group, a sulfite group, a hydrogen sulfate group and a phosphate group, an ammonium salt, and an amine salt; Examples thereof include low molecular weight water-soluble organic acid salts such as citrate and fumarate. Of these, salts having a carbonate group, a sulfate group, and a sulfite group are preferred. The water-soluble salts may be composed of a single component or may be composed of a plurality of components.

Regarding the physical properties of the base granules suitable for the step (A), the bulk density is preferably 400 to 10
00 g / L, more preferably 500-800 g / L, and the average particle size is preferably 150-500 μm,
More preferably, it is 180 to 350 μm. The bulk density is
It is measured by the method of JIS K 3362. The average particle size is
After shaking for 5 minutes using a standard sieve of JIS Z 8801, it is measured from the weight fraction based on the sieve size.

In general, in order to support a large amount of the surfactant composition on the base particles, it is necessary to improve the supporting ability of the base particles. As a method thereof, the ratio of the water-soluble polymer which easily forms a film on the surface of the base granule can be reduced, but the cleaning performance of the obtained detergent composition is reduced. In addition, acrylic acid-maleic acid copolymer, which is particularly effective for cleaning performance, has a strong effect on the crystallization of inorganic salts contained in the slurry, and may reduce the oil absorption capacity of the base particles, and may reduce Attention must be paid to the type and content of the water-soluble polymer incorporated therein. In contrast, the surfactant composition of the present invention
Since the water-soluble polymer can be blended in a high amount, the cleaning performance of the detergent composition obtained using the polymer can be improved.

The mixer used in the step (A) preferably has, for example, a nozzle for adding a surfactant composition and a jacket for controlling the temperature inside the mixer.

The preferable mixing time (in the case of a batch type) and the average residence time (in the case of a continuous type) are, for example, preferably 1 to 20 minutes, more preferably 2 to 10 minutes.

In the step (A), the components (b), (c-1) and (d) are added to the surfactant composition of the present invention.
When an unneutralized component is contained, it may be neutralized with an alkali component in the powdery substance.

In the present invention, by carrying out the step (B) after the step (A), the fluidity and caking resistance of the detergent particles can be improved. When the mixture obtained in the step (A) is not in the form of a powder, the step (B) includes a step of pulverizing the mixture by using a fine powder as an auxiliary agent.

The fine powder improves the coverage of the surface of the detergent particles,
In terms of improving the fluidity and caking resistance of the detergent particles,
The primary particles preferably have an average particle size of 10 μm or less. The average particle size is measured by a method using light scattering, for example, a particle analyzer (manufactured by HORIBA, Ltd.) or microscopic observation.

As the fine powder, aluminosilicate is desirable, and calcium silicate, silicon dioxide, bentonite,
Talc, clay, amorphous silica derivatives, inorganic fine powder such as silicate compounds such as crystalline silicate compounds,
Metal soap having primary particles of 10 μm or less can also be used. In addition, it is preferable that the fine powder has a high ion exchange ability and a high alkali ability in terms of detergency. These fine powders can be used as a mixture of two or more kinds.

The amount of the fine powder used is preferably 0.5 to 40 parts by weight, more preferably 1 to 100 parts by weight, in terms of fluidity and feeling of use, based on 100 parts by weight of the mixture obtained in step (A).
-30 parts by weight, particularly preferably 2-20 parts by weight.

The mixer used in the step (B) is preferably provided with, for example, a high-speed rotating crushing blade in the mixer, from the viewpoint of improving the dispersibility of the fine powder to be added and the crushing efficiency.

The temperature inside the mixer may be set arbitrarily according to the purpose. However, the penetration hardness of the surfactant composition of the present invention is reduced from the viewpoint of reducing the amount of added fine powder and improving the crushing efficiency. Is preferably 100 g / cm ² or more.

The following properties are suitable for the physical properties of the powder detergent composition obtained by such a method. (1) The bulk density is preferably 500 to 1000 g / L,
More preferably, it is 600 to 1000 g / L, particularly preferably 650 to 850 g / L. The method for measuring the bulk density is the same as that for the base granules.

(2) The average particle size is preferably 150 to 5
It is 00 μm, more preferably 180 to 350 μm.
The method for measuring the average particle size is the same as that for the base granules.

(3) The form is preferably a group of mononuclear detergent particles. Here, the mononuclear detergent particles group is an aggregate of detergent particles manufactured using the base granules as a core,
Substantially an aggregate of detergent particles having one base granule as a core in one detergent particle.

As an index indicating the mononuclear property of the detergent particle group, a particle growth rate defined by the following equation can be used. The mononuclear detergent particles as referred to herein have a particle growth rate of preferably 1.5 or less, more preferably 1.3 or less, particularly preferably 1.2 or less. Particle growth rate = average particle size of detergent particles / average particle size of base particles

Since the mononuclear detergent particles are prevented from agglomerating among the particles, particles (agglomerated particles) outside the desired particle size range are not generated, and a detergent particle excellent in solubility is obtained. Has the advantage of being

(4) Regarding the caking resistance, the sieve passing rate is preferably 90% or more, more preferably 95% or more.
As a test method for the anti-cakeing property, a box without a top portion having a height of 10.2 cm × 6.2 cm × 4 cm in height is made with filter paper (“No. 2” manufactured by ADVANTEC), and four corners are stapled. A 50 g sample is put on the box, and an acrylic resin plate (15 g) and a lead plate (250 g) are placed thereon. This is determined by obtaining the following transmissivity for the caked state after being left for two weeks in an atmosphere at a temperature of 35 ° C. and a humidity of 40%.

<Passage> The sample after the test was sieved (JIS
The powder was gently placed on a mesh (defined by Z 8801, 4760 μm), and the weight of the passed powder was weighed to determine the transmittance (%) of the sample after the test.

(5) Adhesion of nonionic surfactant-containing powder to equipment in a transport system if the stain removal property is evaluated by the following test method is preferably at least 2 ranks, more preferably 1 rank. This is preferable because it is not necessary to devise prevention and prevention of stains on the container. Testing method for stain removal property: The stain removal state at the bottom (non-contact surface with powder) of the filter paper container subjected to the caking resistance test was visually evaluated. The evaluation was made based on the wetted area of the bottom, and the following 1 to 5 ranks were used. Rank 1: Not wet. Rank 2: About 1/4 surface was wet. Rank 3: About 1/2 surface was wet. Rank 4: About 3/4 surface was wet. Rank 5: The entire surface was wet.

The detergent composition having the above properties is
It has excellent detergency and can be suitably used as a detergent for general clothing.

[0066]

In the table, abbreviations used in the text are as follows. NI: nonionic surfactant, here polyoxyethylene alkyl ether (trade name: Emulgen 108KM)
(Manufactured by Kao Corporation), melting point: 18 ° C, average number of moles of ethylene oxide added: 8.5, carbon number of alkyl chain: 12 to 12
14) [Component (a)]. DBS: Dodecylbenzenesulfonic acid (trade name: Neoperex FS (manufactured by Kao Corporation) [acid precursor of component (b)] FA: Saturated fatty acid, here palmitic acid (trade name: LUNAC P-95 (Kao) [Fixing agent 1: (c-
1) Acid precursor of component]. PEG: polyethylene glycol (trade name: K-PEG
6000 (manufactured by Kao Corporation), average molecular weight: 8500, melting point: 60 to 66 ° C) [Fixing agent 2: component (c-2)]. PAS: sodium polyacrylate (average molecular weight: 10
000, effective component: 50%) [(d) component]. PAMS: sodium salt of acrylic acid-maleic acid copolymer (average molecular weight: 70000, effective component: 50%)
[(D) component]. Base granules (composition: zeolite / Na polyacrylate /
Na carbonate / Na sulfate / water = 50/10/20/15/5
(Weight ratio) spray-dried particles (bulk density: 620 g / L, average particle size: 225 μm)). Fine powder: crystalline aluminosilicate (zeolite 4A type,
An average aluminosilicate (average particle size of 3.5 μm) and an amorphous aluminosilicate (preparation example 2 described in JP-A-9-132794) pulverized to an average particle size of 8 μm, composition: Na ₂ O · Al ₂ O
₃ · 3SiO ₂₎ and a 1: 1 (in a mixing ratio by weight).

Examples 1-3 Neutralization loop reactor (tube inner diameter 54.1 mm, tube length 7.9)
Using m), a surfactant composition containing component (a), component (b), component (c) and component (d) was prepared.
The loop reactor was essentially closed-loop, with an in-line mixer in the loop. Downstream of the mixer there is a heat exchange device and upstream of the mixer N
I, DBS, sodium hydroxide aqueous solution, PEG, PAS
And a PAMS supply port. An outlet for discharging the mixed liquid was provided downstream of the heat exchange device.
The reactor was equipped with a jacket and could be kept warm.

First, the loop was filled with NI. Then, DBS, 48% by weight sodium hydroxide aqueous solution, PE
G, PAS and PAMS are continuously added into the loop,
After operating the reactor to neutralize and mix these components, FA was added to the mixture discharged from the loop to obtain a surfactant composition. Therefore, in this example, the apparatus was configured such that a supply port for adding the acid precursor of FA and a mixing tank or an in-line mixer for mixing were connected to the outlet of the loop reactor.

As shown in Table 1, other composition parts by weight were determined based on 100 parts by weight of NI, and supply conditions were set. The addition amount of the 48% by weight aqueous sodium hydroxide solution as a neutralizing agent was set so as to be sufficient to neutralize DBS and FA. Operation of loop reactor (jacket)
The temperature was adjusted to maintain 90 ° C. Circulation ratio is 5
Doubled. Further, when FA was stirred in a mixing tank or neutralized with an in-line mixer, there was no particular problem in both the production operation and the physical properties of the obtained composition.

Comparative Example 1 As shown in Table 1, a surfactant composition containing neither PAS nor PAMS was obtained by the same production method and production conditions as described above.

[0071]

[Table 1]

Next, using the surfactant compositions obtained in Examples 1 to 3 and Comparative Example 1, a powder detergent composition was obtained according to the following production method. 100 parts by weight of the base granules were put into a Lodige mixer (manufactured by Matsuzaka Giken Co., Ltd., capacity 130 L, with jacket), and rotation of the main shaft (60 rpm) was started. At this time, the chopper was not rotated, and hot water of 80 ° C. was flowed through the jacket at 10 L / min. 80 ° C there
Sprayed 35 minutes by weight of the surfactant composition heated to a temperature of 2 minutes (manufactured by Spraying Systems Japan KK, "TP
80015-SS ", spray pressure: 2.8kg / cm ^2),
Thereafter, stirring was performed for 5 minutes. Subsequently, while continuously supplying hot water to the jacket, 10 parts by weight of the fine powder was charged into the mixer, and the main shaft (rotation speed: 120 rpm) and the chopper (rotation speed: 3600 rpm) were rotated for 1 minute.
The powdered detergent composition was discharged and obtained. Table 2 shows the properties of the obtained powder detergent composition. The measuring method of each characteristic is as described above.

The method for evaluating the cleaning performance of the obtained powder detergent composition is described below. First, an artificially contaminated cloth having the following composition was adhered to a cloth for cleaning evaluation to prepare an artificially contaminated cloth. The adhesion of the artificially contaminated liquid to the cloth was performed by printing the artificially contaminated liquid on the cloth using a gravure roll coater according to Japanese Patent Application Laid-Open No. 7-273951. The process of preparing the artificially contaminated cloth by adhering the artificially contaminated liquid to the cloth includes a gravure roll cell capacity of 58 cm ³ / cm ² , a coating speed of 1.0 m / min, and a drying temperature of 1.
The drying was performed at 00 ° C. for 1 minute. The cloth used was a cotton gold cloth 2003 (manufactured by Tanito Shoten). The composition of the artificial contaminated liquid is lauric acid
0.44% by weight, myristic acid 3.09% by weight, pentadecanoic acid
2.31% by weight, palmitic acid 6.18% by weight, heptadecanoic acid
0.44% by weight, stearic acid 1.57% by weight, oleic acid 7.75
Weight%, trioleic acid 13.06 weight%, palmitic acid n
2.18% by weight of hexadecyl, 6.53% by weight of squalene, 1.94% by weight of egg white lecithin liquid crystal material, 8.11% by weight of Kanuma red clay, 0.01% by weight of carbon black, and the balance amount of tap water.

The cleaning conditions and the method of evaluating the cleaning power are as follows. Matsushita Electric Industrial washing machine "Aisuma-go NA-
F70AP "2.2kg of clothing (underwear / Y-shirt = 8/2 (weight ratio)) and 10cm x 10cm produced above
10 artificially contaminated cloths of 35cm x 30cm cotton base cloth 3
The pieces were sewed uniformly and placed uniformly, and 22 g of the powdered detergent composition was placed on clothing in a gathered state, and the powdered detergent composition was washed without being directly hit by water, and washed. The washing conditions were such that the washing course of the washing machine was a standard course, the detergent concentration was 0.067%, the water hardness was 4 ° DH, the water temperature was 20 ° C., and the bath ratio was 15 L / kg. The detergency is 55% of the original cloth before and after cleaning.
The reflectance at 0 nm was measured with a self-recording colorimeter (manufactured by Shimadzu Corporation), and the cleaning rate (%) was determined by the following formula. Cleaning rate (%) = (Reflectance after cleaning−Reflectance before cleaning) /
(Reflectance of original cloth-Reflectance before washing) × 100

The powder detergent compositions obtained from the surfactant compositions of Examples 1 to 3 and Comparative Example 1 were evaluated according to the above-described method for evaluating the cleaning performance. Table 2 shows the results.

[0076]

[Table 2]

From the results in Table 2, it was found that PAS and / or PAM
The detergency of the powder detergent compositions obtained from the surfactant compositions containing S (Examples 1 to 3) is better than that of the powder detergent compositions obtained from those without these (Comparative Example 1). You can see that.

[0078]

According to the present invention, the composition has low viscosity (fluidity) enough to be easily handled in the temperature range at the time of production, while it has non-ionicity in the temperature range at the time of storage of the detergent composition. It is possible to efficiently provide a surfactant composition having the property that the surfactant composition cures in order to suppress spotting of the surfactant and improve the strength of the detergent composition. Further, using this, a powder detergent composition with less stain of the nonionic surfactant and excellent detergency in addition to anti-caking properties can be produced.

[Brief description of the drawings]

FIG. 1 shows a surfactant composition (X) containing a component (a), a component (b) and a component (d), and (a)
It is a figure which shows the relationship between temperature (degreeC) and penetration hardness (g / cm < ² >) about the composition (Y) containing a component, (b) component, (c) component, and (d) component. . T ₁ is (a)
The melting points of the components, T ₂ indicates the pour point of the composition (Y), L indicates the data of the composition (X), and M indicates the data of the composition (Y).

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C11D 3/12 C11D 3/12 11/04 11/04 17/06 17/06 (72) Inventor Hiroyuki Yamashita 1334 Minato, Wakayama-shi Kao Research Laboratory F-term (reference) 4H003 AB03 AB19 AC08 BA09 DA01 EA12 EA16 EA28 EB06 EB30 EB32 ED02 FA16 FA41

Claims (6)

[Claims] 1. A nonionic surfactant having a melting point of 30 ° C. or lower (component (a)), an anionic surfactant having a sulfate group or a sulfonic acid group (component (b)), and a component (a). It comprises a fixing agent (component (c)) and a polymer having a carboxyl group (component (d)), wherein the component (c) has a carboxyl group or a phosphate group but has a sulfate group or a sulfonic acid group. At least one selected from the group consisting of anionic surfactants (component (c-1)) and compounds having a melting point of 35 ° C. or higher (component (c-2)) compatible with component (a). A surfactant composition comprising (a) component 1
The content of the component (b) is 10 to 300 parts by weight with respect to 00 parts by weight.
Parts by weight, the content of the component (c) is 1 to 100 parts by weight,
(D) the content of the component is 1 to 100 parts by weight, and at a temperature not lower than the pour point of the surfactant composition, the composition has a temperature range in which the viscosity of the composition is 10 Pa · s or less; A surfactant composition having a temperature range in which the penetration hardness of the composition is 100 g / cm ² or more in a temperature range lower than the pour point of the product and higher than the melting point of the component (a). 2. The surfactant composition according to claim 1, wherein the component (d) is a homopolymer and / or a copolymer of acrylic acid having a molecular weight of 1,000 to 100,000. 3. The method for producing a surfactant composition according to claim 1, wherein the acid precursor of the component (b) is used in the presence of the component (a) in a liquid form using a loop reactor. A method for producing a surfactant composition comprising a step of neutralizing with a surfactant. 4. An acid precursor of the component (c-1) after neutralizing a composition comprising components other than the acid precursor of the component (c-1) with a liquid alkali compound using a loop reactor. 4. The method according to claim 3, wherein the neutralization is carried out by adding a compound. 5. A powder detergent composition comprising 100 to 2000 parts by weight of a powdery substance per 100 parts by weight of the surfactant composition according to claim 1 or 2. 6. A powder detergent composition comprising the step of mixing the surfactant composition according to claim 1 or 2 with a powdery substance at a temperature at which the viscosity of the surfactant composition is 10 Pa · s or less. Manufacturing method.