JP5718168B2 - Method for producing detergent composition - Google Patents

Description

  The present invention relates to a surfactant composition containing an alkyl sulfate (hereinafter also referred to as AS) and a specific nonionic surfactant. Furthermore, this invention relates to the manufacturing method of the detergent composition containing this surfactant composition.

  Major anionic surfactants used in powder detergents include alkylbenzene sulfonates and alkyl sulfates. Alkyl sulfate is a surfactant using natural alcohol as a raw material, and has a very high carbon ratio derived from nature as compared with alkylbenzene sulfonate produced from a petrochemical raw material.

  However, in the process of industrially producing a detergent composition by supporting a surfactant composition comprising an alkyl sulfate, a nonionic surfactant and water on a powder raw material, the heat of the sulfate ester group In order to suppress decomposition, it is necessary to formulate at a low temperature (60 ° C.). However, since the effective amount of the alkyl sulfate is about 60%, the amount of water brought in at the time of preparing the surfactant composition is increased, and therefore, there is a possibility that the structure is formed and the viscosity is increased at a low temperature (60 ° C.). is there. When the surfactant composition is thickened, poor oil absorption to the powder raw material occurs, which may affect the powder physical properties and low-temperature solubility of the detergent composition.

  On the other hand, as an invention related to a powder detergent using an alkyl sulfate having such characteristics, for example, in Patent Document 1, it comprises a nonionic surfactant and an alkylbenzene sulfonate or an alkyl sulfate and water. A surfactant composition used for the production of a powder detergent having mobility that can be sprayed in the range of 20 to 80 ° C. is disclosed.

Japanese Unexamined Patent Publication No. 63-110292

  However, Patent Document 1 does not specifically describe the examples using alkyl sulfates, and suggests any description about the low-temperature solubility of powder detergents when alkyl sulfates are used. It has not been done. Furthermore, when alkyl sulfate is used and a surfactant is used in the vicinity of the high temperature (80 ° C.) in the temperature range of Patent Document 1, there is no description about the problem that the thermal decomposition of the sulfate ester group occurs in a short period of time. There is no suggestion. Furthermore, regarding the thickening of the surfactant composition due to the formation of a structure near low temperature (60 ° C.) and the deterioration of the powder properties and low temperature dispersibility of the detergent composition as the final product due to poor loading on the powder raw material However, there is no description or suggestion.

  Accordingly, an object of the present invention is to provide a surfactant composition containing an alkyl sulfate that can be formulated even at a low temperature such as 60 ° C., and impregnating the surfactant composition with a powder raw material. It is intended to provide a method for producing a detergent composition having excellent low-temperature solubility and low-temperature dispersibility.

That is, the gist of the present invention is as follows.
[1] (a): 5-50% by mass of alkyl sulfate,
(B): The following general formula (1):
RO - _{[(PO) m / (EO)} n ] -SO ₃ M (1)
(In the formula, R is a hydrocarbon group, PO and EO are a propyleneoxy group and an ethyleneoxy group, respectively, m and n are the average added moles of PO and EO, respectively, and 0 ≦ m ≦ 5 and 0 <n ≦ 5, “/” is a symbol indicating that the bonding mode of PO and EO may be random addition or block addition, and M is a cation.) 0-50 mass% of sulfate ester salt,
(C): After adding p ₁ mol of ethylene oxide to 1 mol of the compound represented by the formula: R ¹ OH (R ¹ is a hydrocarbon group having 8 to 18 carbon atoms), the number of carbon atoms is 3 A nonionic surfactant obtained by adding ₁ mol of alkylene oxide of ˜5 and then adding ₂ mol of ethylene oxide, wherein p ₁ is a number from 3 to 30, and p ₂ is 1 40 to 70% by mass of a nonionic surfactant having q _{1 of 1} to 5 and p ₁ + p ₂ = 16 to 50, and (d): containing water A surfactant composition comprising:
The amount of component (d) is such that the surfactant composition does not form a structure at 60 ° C.
A surfactant composition having a viscosity at 60 ° C. of 0.8 Pa · s or less;

[2] (a): 5 to 50% by mass of alkyl sulfate,
(B): 0-50 mass% of alkyl ether sulfate ester salt represented by the above general formula (1),
(C): After adding p ₁ mol of ethylene oxide to 1 mol of the compound represented by the formula: R ¹ OH (R ¹ is a hydrocarbon group having 8 to 18 carbon atoms), the number of carbon atoms is 3 A nonionic surfactant obtained by adding ₁ mol of alkylene oxide of ˜5 and then adding ₂ mol of ethylene oxide, wherein p ₁ is a number from 3 to 30, and p ₂ is 1 40 to 70% by mass of a nonionic surfactant having q _{1 of 1} to 5 and p ₁ + p ₂ = 16 to 50, and (d): containing water A surfactant composition comprising:
The ratio [(d) / (c)] of component (d) and component (c) is 0.01 to 0.7 (mass ratio),
The ratio [(d) / ((a) + (b))] of the component (d) to the total amount of the component (a) and the component (b) is 0.3 to 1.3 (mass ratio),
A surfactant composition having a viscosity at 60 ° C. of 0.8 Pa · s or less;

[3] having a step of supporting the surfactant composition according to [1] or [2] on a powder raw material in a range of 40 to 70 ° C., having an average particle diameter of 150 to 500 μm, and having a bulk density And a detergent composition produced by the production method according to [3] above, and [4] the detergent composition produced by the production method according to [3] above.

  By using the surfactant composition of the present invention comprising an anionic surfactant containing an alkyl sulfate, a nonionic surfactant having a specific structure, and water, a nonionic interface at a low temperature Suppressing the structuralization such as gelation of the active agent, suppressing the thickening of the surfactant composition, and promoting the penetration of the surfactant composition into the powder raw material under low temperature conditions. The effect of providing a detergent composition excellent in low-temperature solubility and low-temperature dispersibility is exhibited. In addition, by using the nonionic surfactant, it can be formulated even when the amount of water during preparation of the surfactant composition is large, so it is conventionally necessary to suppress gelation. The effect that the dehydration process which existed can be skipped is also show | played.

FIG. 1 is a diagram showing the results of analyzing the surfactant compositions of Example 2 and Comparative Example 1 using a two-dimensional image X-ray diffractometer at 60 ° C. FIG.

1. Ingredient (a)
Component (a) is an alkyl sulfate, and the alkyl group preferably has 8 to 20 carbon atoms, more preferably 12 to 15 carbon atoms. The alkyl group may be linear or branched, but is preferably linear. The counter ion of alkylsulfuric acid is not particularly limited, and examples thereof include sodium ion, potassium ion, and ammonium ion.

  The amount of the component (a) in the surfactant composition is 50% by mass or less, and preferably 35% by mass or less from the viewpoints of detergency at low temperatures and handling properties of the surfactant composition. Moreover, the quantity of a component (a) is 5 mass% or more, and it is preferable that it is 10 mass% or more from the point of the storage stability of a detergent composition, and it is more preferable that it is 15 mass% or more.

2. Ingredient (b)
In the present invention, it is preferable to use the component (b) from the viewpoint of improving the surface modification property, detergency and low-temperature solubility of the detergent composition. Component (b) is represented by the following general formula (1):
RO - _{[(PO) m / (EO)} n ] -SO ₃ M (1)
(In the formula, R is a hydrocarbon group, PO and EO are a propyleneoxy group and an ethyleneoxy group, respectively, m and n are the average added moles of PO and EO, respectively, and 0 ≦ m ≦ 5 and 0 <n ≦ 5, “/” is a symbol indicating that the bonding mode of PO and EO may be random addition or block addition, and M is a cation.) It is a sulfate ester salt. In the general formula (1), the order of bonding of PO and EO is not particularly limited, and examples include those obtained by random addition and those obtained by block addition.

  Examples of the hydrocarbon group for R include an alkyl group and / or an alkenyl group, and an alkyl group is preferable. The carbon number of R is preferably 8-20, more preferably 12-15. The hydrocarbon group may be linear or branched.

  From the viewpoint of surface modification property, detergency and low-temperature solubility of the detergent composition, a more preferable range of m is 0 ≦ m ≦ 3, a more preferable range is 0 ≦ m ≦ 1, and a more preferable range is m. = 0. Further, from the viewpoint of surface modification property, detergency and low-temperature solubility of the detergent composition, a more preferable range of n is 0.5 ≦ n ≦ 4, and a more preferable range is 1 ≦ n ≦ 3. A preferred range is 1.5 ≦ n ≦ 2.5.

  The preferred ranges for m and n are the numbers 0 ≦ m ≦ 3 and 0.5 ≦ n ≦ 4, and the more preferred ranges are the numbers 0 ≦ m ≦ 1 and 1 ≦ n ≦ 3, and still more preferred ranges. Is a number where m = 0 and 1.5 ≦ n ≦ 2.5.

  M is not limited as long as it is a cation, and examples thereof include sodium ion, potassium ion, and ammonium ion.

  The amount of component (b) in the surfactant composition is 0 to 50% by mass, but when component (b) is used, the amount of component (b) in the surfactant composition is 50% by mass or less. Yes, preferably 30% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less, preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more. It is. Furthermore, from the viewpoint of the surface modification property and detergency of the detergent composition, the total amount of the component (a) and the component (b) is preferably 10 to 50% by mass, more preferably 15 to 40% by mass, 20-30 mass% is further more preferable.

3. Ingredient (c)
Component (c) is a nonionic surfactant having a specific structure, that is, 1 mol of a compound represented by the formula: R ¹ OH (R ¹ is a hydrocarbon group having 8 to 18 carbon atoms). per, after ethylene oxide p ₁ mol adduct, after an alkylene oxide having 3 to 5 carbon atoms is q ₁ mol adduct, a further non-ionic surfactant obtained was p ₂ moles addition of ethylene oxide , P ₁ is a number of 3 to 30, p ₂ is a number of 1 or more, q ₁ is a number of ₁ to 5, and p ₁ + p ₂ = 16 to 50. is there.

R ¹ in the above formula is a hydrocarbon group having 8 to 18 carbon atoms, preferably 10 to 16 carbon atoms, more preferably 12 to 14 carbon atoms from the viewpoint of stability and detergency. From the viewpoint of detergency, the oxygen atom bonded to R ¹ is preferably bonded to the first carbon atom or the second carbon atom of R ¹ . Component (c) can be obtained by adding an alkylene oxide to a primary or secondary alcohol. R ¹ is preferably an alkyl group or an alkenyl group, and more preferably a straight chain.

As a raw material for obtaining such a compound having R ¹ , it is preferable to use an alcohol derived from a natural fat that is a primary alcohol. In this case, R ¹ is usually composed of an even number of carbon atoms having 8 to 18 carbon atoms, and may be composed of an alkyl distribution of a natural fatty acid, but in the present invention, in particular, an alkyl group having 12 carbon atoms. And one or more linear alkyl groups selected from alkyl groups having 14 carbon atoms. Since p ₁ , p ₂ , and q ₁ are the number of moles added per mole of the compound represented by R ¹ OH, these may be hereinafter described as the average number of moles added.

The component (c) in this invention can be shown as a nonionic surfactant represented by the following general formula (I).
R ¹ O— (EO) p ₁ (AO) q ₁ (EO) p ₂ H (I)
[Wherein R ¹ represents a hydrocarbon group having 8 to 18 carbon atoms, EO represents an ethyleneoxy group, AO represents an alkyleneoxy group having 3 to 5 carbon atoms, and p ₁ and p ₂ represent average additions of EO, respectively. The number of moles, p ₁ is a number of 3 to 30, p ₂ is a number of 1 or more, q ₁ is the average number of moles of AO added, and is a number of 1 to 5. p ₁ + p ₂ = 16-50. ]

The average added mole number p ₁ of EO in the component (c) is 3 to 30, preferably 6 to 20, and more preferably 8 to 15. The average addition molar number p ₂ of EO, relative to p ₁ in such a range, but p ₁ + p ₂ is a number which is a 16 to 50, p ₂ is 1 or more, preferably 3 to 30, More preferably, it is 6-20, More preferably, it is 8-15.

The total p ₁ + p ₂ of average added moles of EO in the component (c) is 16 to 50, preferably 16 to 40, more preferably 17 to 30, even more preferably 18 to 25, and 18 to 20 Is more preferable. When p ₁ + p ₂ is 16 or more, and further 18 or more, liquid crystal formation at a low temperature is suppressed, and the solubility is improved. This is presumably because the size of the hydrophilic group portion of the surfactant becomes relatively large compared to the size of the hydrophobic group portion, and the alignment of the surfactant is suppressed. Further, when p ₁ + p ₂ is 50 or less, further 40 or less, further 30 or less, further 25 or less, particularly 20 or less, the cleaning performance and the stability at low temperature are improved.

The average added mole number q ₁ of the alkyleneoxy group having 3 to 5 carbon atoms in the component (c) is ₁ to 5, preferably 2 to 4, more preferably 2 to 3.

The average added mole number q ₁ of AO is 1 or more in terms of excellent liquid crystal and crystal formation inhibiting ability, solubility, and stability at low temperature, and 5 or less in terms of cleaning performance. AO is obtained by adding an alkylene oxide having 3 to 5 carbon atoms. AO is not only common in that it has a branched alkyl group, but EO is known to block to form a hydrophilic site, while AO is known to exhibit lipophilicity. ing. Among AOs, an alkyleneoxy group having 3 carbon atoms, that is, a propyleneoxy group is preferred not only for versatility but also for the ease of the subsequent addition reaction of ethylene oxide.

As an index indicating the positional relationship between AO and EO in the component (c), the ratio of the average added mole numbers p ₁ and p ₂ of EO is preferably p ₁ / (p ₁ + p ₂ ) = 0.2 to 0.8. More preferably, it is 0.3-0.7, More preferably, it is 0.4-0.6. When p ₁ / (p ₁ + p ₂ ) is 0.2 or more, the ability to suppress liquid crystal and crystal formation is improved, so that the solubility and stability at low temperature are improved. When p ₁ / (p ₁ + p ₂ ) is 0.8 or less, the ability to suppress crystal formation is improved, so that stability at low temperatures is improved.

  The amount of the component (c) in the surfactant composition is 40 to 70% by mass, and preferably 45 to 60% by mass from the viewpoints of detergency at low temperatures and handling properties of the surfactant composition.

4). Ingredient (d)
Component (d) is water. The amount of component (d) is water in such an amount that the surfactant composition does not form a structure at 60 ° C. Here, the structure is not particularly limited, but refers to, for example, a state in which a part or the whole of the surfactant composition is gelled or crystallized.

  The structural analysis of the surfactant composition is performed, for example, by using a two-dimensional image X-ray diffractometer PINT PAPID (Rigaku Co., Ltd.) and measuring at a temperature at which the surfactant composition is actually used (for example, 60 ° C.). Can be implemented. More specifically, a surfactant composition that does not form a structure is a peak having a 2θ of 1.5 to 3.0 and an intensity ratio with the baseline of 2.0 or more, more preferably 1. It is defined as having no more than 5 peaks, more preferably no more than 1.3 peaks.

  Regarding the amount of component (d), specifically, the mass ratio [(d) / (c)] of water as component (d) to component (c) is the structure formation of the surfactant composition. 0.7 or less is preferable from the viewpoint of prevention, 0.6 or less is more preferable, 0.5 or less is preferable from the viewpoint of the cleaning performance of the surfactant composition, 0.4 or less is more preferable, 0.35 or less Is more preferable. Furthermore, from the viewpoint of structure formation prevention and cleaning performance of the surfactant composition containing AS, [(d) / (c)] is preferably 0.01 or more, more preferably 0.05 or more, and 1 or more is more preferable, and 0.2 or more is more preferable. From this, the range of [(d) / (c)] is preferably from 0.01 to 0.7, and preferably from 0.05 to 0.00 as a range in which gelation and prevention of crystallization of the surfactant composition can both be achieved. 4 is more preferable, and 0.1 to 0.35 is still more preferable.

  Regarding the amount of component (d), the ratio of component (d) to the total amount of component (a) and component (b) [(d) / (a) + (b)] (mass ratio) is: From the viewpoint of preventing the formation of the structure of the surfactant composition containing AS, 1.3 or less is preferable, 1.0 or less is more preferable, 0.8 or less is more preferable, and 0.3 or more is preferable. Moreover, 0.3-0.8 are preferable and 0.35-0.65 are more preferable.

  The component (a), the component (b) and / or the component (c) may be added in a state using water as a medium, for example, in the form of an aqueous solution. In such a case, water as a medium is used as the component (d). Are treated as As a matter of course, water as the component (d) may be added separately from the component (a), the component (b) or the component (c).

Accordingly, one preferred embodiment of the surfactant composition of the present invention includes the following.
(A): 5-50 mass% of alkyl sulfate,
(B): The following general formula (1):
RO - _{[(PO) m / (EO)} n ] -SO ₃ M (1)
(In the formula, R is a hydrocarbon group, PO and EO are a propyleneoxy group and an ethyleneoxy group, respectively, m and n are the average added moles of PO and EO, respectively, and 0 ≦ m ≦ 5 and 0 <n ≦ 5, “/” is a symbol indicating that the bonding mode of PO and EO may be random addition or block addition, and M is a cation.) 0-50 mass% of sulfate ester salt,
(C): After adding p ₁ mol of ethylene oxide to 1 mol of the compound represented by the formula: R ¹ OH (R ¹ is a hydrocarbon group having 8 to 18 carbon atoms), the number of carbon atoms is 3 A nonionic surfactant obtained by adding ₁ mol of alkylene oxide of ˜5 and then adding ₂ mol of ethylene oxide, wherein p ₁ is a number from 3 to 30, and p ₂ is 1 40 to 70% by mass of a nonionic surfactant having q _{1 of 1} to 5 and p ₁ + p ₂ = 16 to 50, and (d): containing water A surfactant composition comprising:
The ratio [(d) / (c)] of component (d) and component (c) is 0.01 to 0.7 (mass ratio),
The ratio [(d) / ((a) + (b))] of the component (d) to the total amount of the component (a) and the component (b) is 0.3 to 1.3 (mass ratio),
A surfactant composition having a viscosity at 60 ° C. of 0.8 Pa · s or less.

5. Other components Other components such as a solidifying agent can be added. For example, an anionic surfactant having a carboxylic acid group or a phosphoric acid group (but having a sulfonic acid group) as the component (e-1). And at least one compound selected from the group consisting of polyoxyalkylene-type nonionic compounds and polyether-based nonionic compounds having a melting point of 35 ° C. or higher as component (e-2). be able to.

  More specifically, examples of the component (e-1) include anionic surfactants such as fatty acid salts, hydroxy fatty acid salts, and alkyl phosphates. In particular, one or more selected from amine salts such as sodium and potassium alkali metal salts and alkanolamines of fatty acids having 10 to 22 carbon atoms or hydroxy fatty acids and alkanolamines are preferred in terms of solubility. Particularly preferably, it is at least one selected from sodium and potassium salts of saturated fatty acids having 12 to 18 carbon atoms, preferably 12 to 16 carbon atoms, and more preferably 13 to 15 carbon atoms from the viewpoint of suppressing spotting out.

  The amount of the fatty acid salt used as the component (e-1) is preferably 40 parts by mass or less, more preferably 20 parts per 100 parts by mass of the nonionic surfactant of the component (c) from the viewpoint of solubility. The amount is at most 10 parts by mass, more preferably at most 10 parts by mass.

  Component (e-2) is preferably a compound having a melting point of 35 ° C. or higher and compatible with the nonionic surfactant of component (c). Examples thereof include one or more selected from polyoxyalkylene type nonionic compounds having a molecular weight of 1,000 to 30,000, polyether nonionic compounds having a molecular weight of 1,000 to 30,000, and the like. Particularly preferable examples include polyethylene glycol, polypropylene glycol, and polyoxyethylene alkyl ether. Among them, the effect of increasing the penetration hardness of the composition at a temperature range higher than the melting point of the nonionic surfactant of component (c) and lower than the pour point of the surfactant composition, and at a temperature higher than the pour point. From the viewpoint of improving the effect of reducing the viscosity of the composition, polyethylene glycol having a molecular weight of 1,000 to 10,000 (preferably 1,000 to 5,000) is preferable. The term “compatibility” as used herein refers to a property in which the mixture of the component (c) and the component (e-2) is well mixed at any temperature equal to or higher than the melting point of the component (c), and phase separation is difficult. Therefore, the mixing ratio of the component (e-2) to the component (c) may be set as appropriate within a handleable range.

  Component (e) may be component (e-1) alone or component (e-2) alone, or a mixture of component (e-1) and component (e-2). In particular, the use of the mixture as the component (e) is particularly preferable because it can further improve the anti-smudge effect and the caking resistance. Furthermore, as other components, a polymer such as polyethylene glycol and / or sodium sulfate (sodium sulfate) can be added.

6). Surfactant Composition The surfactant composition of the present invention contains an alkyl sulfate that causes thermal decomposition of sulfate groups at high temperatures. Accordingly, a low temperature range (for example, 40 to 67 ° C., more preferably 65 ° C. or less, further preferably 62 ° C. or less. On the other hand, from the viewpoint of handling, it is preferably 45 ° C. or more, more preferably 50 ° C. or more, and 55 ° C. or more. It is important to prepare, handle and formulate the surfactant composition.

  The surfactant composition can be prepared, for example, as follows. An alkyl sulfate having an effective content of 60 to 70% as component (a), a nonionic surfactant as component (c), and an alkyl ether sulfate ester salt as component (b) as necessary in the temperature range specified above. Mix.

  The viscosity of the obtained surfactant composition can be controlled by the ratio of the nonionic surfactant and the water. For example, if the component (c) is a polyoxyethylene alkyl ether, the water as the component (d) As mass ratio ((d) / (c)) with a component (c), Preferably it is 0.01-0.5, More preferably, it is 0.01-0.5, More preferably, it is 0.05-0. By adjusting the viscosity to 4, more preferably from 0.01 to 0.35, the viscosity can be adjusted to be handled at 60 ° C. or lower.

  The viscosity at 60 ° C. of the surfactant composition is 0.8 Pa · s or less, preferably 0.65 Pa · s or less, more preferably 0.2 Pa · s or less. Moreover, it is preferable that it is 0.02 Pa.s or more. The viscosity was measured using a coaxial double cylindrical rotational viscometer (manufactured by HAAKE, sensor: SV-DIN), and after setting the surfactant composition to a predetermined temperature (60 ° C.), Measurement is started at a shear rate of 50 [1 / s], and the viscosity 5 minutes after the start of measurement is taken as the measured value.

  Therefore, if necessary, the operation of the following (1) or (2) is performed under the condition of 50 to 60 ° C. to adjust the water content in the surfactant composition.

(1) Surfactant composition under reduced pressure (5 to 20 kPa) using a wall / wetter (30 L scale) manufactured by Kansai Chemical Machinery Manufacturing Co., Ltd. or an evaporator (equipment number: CEP-1) manufactured by Okawara Seisakusho A method of further reducing the amount of water in it, for example, removing it to 5 to 12% by mass.
(2) A method of neutralizing alkyl sulfuric acid or alkyl ether sulfate in a nonionic active agent as described in JP-A-64-47755.

7). Detergent Composition Furthermore, one of the objects of the present invention is to provide a detergent composition having excellent low-temperature solubility and low-temperature dispersibility by supporting the prepared surfactant composition by mixing it with a powder raw material under low-temperature conditions. The thing is to make things. Therefore, the manufacturing method of the detergent composition using the surfactant composition of the present invention and the detergent composition manufactured by such manufacturing method are also included in the present invention.

  The most common form of the detergent for clothing is powdery, and in order to obtain a powdery form, the powder raw material is 150 to 2,000 parts by weight with respect to 100 parts by weight of the surfactant composition of the present invention. It is preferable to mix | blend and it is more preferable to mix | blend 200-1,000 mass parts from the point of a detergency. A suitable production method for obtaining a powdery detergent composition comprises the following step (A), and may further comprise a step (B) if necessary.

Step (A): The powder raw material shown below and the viscosity at 60 ° C. are 0.8 Pa · s or less, preferably 0.65 Pa · s or less, more preferably 0.2 Pa · s or less, while preferably 0 A step of obtaining a detergent composition by mixing a surfactant composition having a pressure of 0.02 Pa · s or more under conditions of 40 to 70 ° C. and supporting the surfactant composition on a powder raw material.
Step (B): A step of mixing the detergent composition obtained in the step (A) with the fine powder and coating the surface of the detergent composition with the fine powder. Step (B) includes a case where crushing proceeds simultaneously.

  Here, the powder raw material is not particularly limited, but is a builder (detergent builder) generally used for a detergent for clothing, for example, sequestering agents such as zeolite and citrate, Powders such as alkali agents such as sodium carbonate and potassium carbonate, bases having both metal ion sequestering ability and alkali ability such as crystalline silicate, and granulates composed of these builder alone or plural components means. In addition, other bases generally used in detergent compositions, for example, surfactants known in the field of garment detergents, anti-staining agents such as acrylic acid polymers or acrylic acid maleic acid copolymers and carboxymethyl cellulose, and mirabilite A base granule obtained by drying a slurry appropriately containing an inorganic powder such as sulfite, a fluorescent brightening agent, or the builder is also a kind of powder raw material. Furthermore, clay minerals such as bentonite are a kind of powder raw material.

  When such base granules are used, the amount thereof is preferably 60% by mass or more, more preferably 70% by mass or more, particularly preferably 80% by mass or more, based on the solubility of the detergent composition. Moreover, 100 mass% may be sufficient. However, in the case of a detergent composition containing fine powder, the calculation is performed excluding the amount of fine powder.

  Regarding the physical properties of suitable base granules, the bulk density is preferably 400 to 1000 g / L, more preferably 500 to 800 g / L, and the average particle size is preferably 150 to 500 μm, more preferably 180 to 350 μm. It is. The bulk density is measured by the method of JIS K 3362. The average particle size (Xa) is determined as follows using a sieve specified in JIS Z 8801.

For example, using a 9-stage sieve and a saucer having openings of 2000 μm, 1400 μm, 1000 μm, 710 μm, 500 μm, 355 μm, 250 μm, 180 μm and 125 μm, a low tap machine (made by HEIKO SEISAKUSHO, tapping: 156 times / minute, rolling: 290 times / minute), 100 g of the sample is shaken for 5 minutes and sieved. Thereafter, the mass frequencies of the pan and each sieve are integrated in the order of the pan, 125 μm, 180 μm, 250 μm, 355 μm, 500 μm, 710 μm, 1000 μm, 1400 μm, and 2000 μm. When the opening of the first sieve with an integrated mass frequency of 50% or more is x _j μm, and the opening of the sieve smaller by one is x _{j + 1} μm, the distance from the tray to the x _j μm sieve When the mass frequency integration is Q _j % and the mass frequency integration from the saucer to the x _{j + 1} μm sieve is Q _{j + 1} %, the average particle size (Xa) is expressed by equations (1) and (2). Ask.

  Base granules are prepared by slurry drying. Examples of the drying method include spray drying, freeze drying, thin film drying, vacuum drying, and kneading drying. Of these, spray drying is preferred from the viewpoint of productivity. Further, the base granule may be obtained by pulverizing and classifying after drying.

  The mixer used in the step (A) is preferably, for example, a nozzle provided with a jacket for controlling the temperature inside the nozzle or the mixer for adding the surfactant composition. In step (A), when the surfactant composition of the present invention contains an unneutralized product of component (a) or component (b), it is neutralized with an alkali component in the powder raw material. Also good. A suitable mixing time (in the case of a batch system) and an average residence time (in the case of a continuous system) are preferably, for example, 1 to 20 minutes, and particularly preferably 2 to 10 minutes. Furthermore, by performing a process (B), the fluidity | liquidity and caking resistance of a detergent composition can be improved. Further, when the mixture obtained in the step (A) is not in a powder form, the step (B) includes a step of crushing the mixture using the fine powder as an auxiliary agent.

  The fine powder preferably has an average primary particle size of 10 μm or less from the viewpoint of improving the coverage of the detergent composition surface and improving the flowability and caking resistance of the detergent composition. The average particle diameter is measured by a method using light scattering, for example, a particle analyzer (manufactured by Horiba, Ltd.).

  The fine powder is preferably an aluminosilicate, inorganic fine powder such as a silicate compound such as calcium silicate, silicon dioxide, bentonite, talc, clay, amorphous silica derivative, crystalline silicate compound, or 10 μm of primary particles. The following metal soaps can also be used. The fine powder preferably has a high ion exchange ability and a high alkali ability in terms of detergency.

  The amount of the fine powder used is preferably 0.5 to 40 parts by weight, more preferably 1 to 30 parts by weight, particularly preferably 2 to 2 parts by weight with respect to 100 parts by weight of the powder detergent composition in terms of fluidity and feeling of use. 20 parts by mass.

The mixer used in the step (B) is preferably provided with a crushing blade rotating at high speed in the mixer, for example, from the viewpoint of improving the dispersibility of the fine powder to be added and improving the crushing efficiency.
The temperature in the mixer may be arbitrarily set according to the purpose. However, if the penetration hardness of the surfactant composition of the present invention is in a temperature range of 100 g / cm ² or more, the amount of fine powder added can be reduced and solved. This is advantageous in terms of improving the crushing efficiency.

The following are suitable for the physical properties of the detergent composition.
(1) The dissolution rate of the detergent composition at low temperature is preferably 80% or more, more preferably 90% or more, and still more preferably 95% or more. The method for measuring the dissolution rate is as follows.

1 L hard water (Ca / Mg molar ratio 7/3) equivalent to 71.2 mg CaCO ₃ / L cooled to 5 ° C. in a 1 L beaker (inner diameter 105 mm, height 150 mm cylindrical type, for example, 1 L manufactured by Iwaki Glass Co., Ltd.) Filled into a glass beaker), with a water bath kept at a constant temperature of 5 ° C., a stirrer (length 35 mm, diameter 8 mm, for example, model: ADVANTEC, Teflon (registered trademark) round thin type) And stirring at a rotational speed (800 rpm) at which the depth of the spiral with respect to the water depth is about 1/3. The target detergent composition, which has been reduced and weighed to 1.000 ± 0.0010 g, is added to and dispersed in water with stirring, and stirring is continued. Sixty seconds after the addition, the dispersion of the detergent composition in the beaker was filtered through a standard sieve (diameter 100 mm) having a known aperture of 74 μm with a JIS Z 8801 (corresponding to ASTM No. 200) with a known mass, and remained on the sieve. The water-containing detergent composition is collected together with a sieve in an open container of known mass.

  The operation time from the start of filtration until the sieve is collected is 10 ± 2 seconds. The collected residue of the detergent composition is dried in an electric dryer heated to 105 ° C. for 1 hour, and then kept in a desiccator (25 ° C.) containing silica gel for 30 minutes for cooling. After cooling, the total mass of the dry detergent residue, sieve and collection container is measured, and the dissolution rate (%) of the detergent composition is calculated by the following formula. The mass is measured using a precision balance.

Dissolution rate (%) = {1- (T / S)} × 100
[S: input mass of target detergent composition (g); T: dry mass of dissolved residue of target detergent composition remaining on sieve after subjecting aqueous solution obtained under above stirring conditions to above sieve ( g) (Drying conditions: After holding the sieve at a temperature of 105 ° C. for 1 hour, hold it in a desiccator (25 ° C.) containing silica gel for 30 minutes.) ]

(2) Evaluation method of dispersibility (paste formation, paste remaining rate) at low temperature is as follows.
17.5 g of a detergent composition is placed in an aggregated state near one outer periphery of a fan-shaped depression divided into six parts of a pulsator of a Panasonic washing machine “Aizuma No. NA-F42Y1”. Next, 22 L of tap water of 5 ° C. is poured at a flow rate of 10 L / min so that the detergent composition is not directly exposed to water, and left standing after the pouring is completed. Five minutes after the end of pouring, stirring is started with a weak water flow (hand washing mode), and after stirring for 3 minutes, the water is drained, and the state of the detergent remaining in the washing tub is determined according to the following evaluation criteria. The “residual particle area” described below refers to the total area when the remaining detergent particles are spread in a container having a flat bottom.

[Evaluation criteria for paste formability]
I: There is no aggregate or is not visible.
II: Almost no aggregates (residual particle area within 25 mm ² ).
III: (100 mm ² within beyond residual particle area 25 mm ²⁾ which agglomerates remaining small amount.
IV: A large amount of aggregate remains (residual particle area exceeds 100 mm ² ).

(3) The bulk density is preferably 500 g / L or more, more preferably 500 to 1000 g / L, further preferably 600 to 900 g / L, and still more preferably 650 to 850 g / L. The method for measuring the bulk density is the same as that for the base granule.

(4) The average particle diameter is preferably 150 to 500 μm, more preferably 200 to 450 μm, and still more preferably 250 to 400 μm. The method for measuring the average particle size is the same as that for the base granule.

(5) The caking resistance is preferably such that the sieve passing rate is 90% or more, more preferably 95% or more. The test method of caking resistance is to make a box without a top of 10.2 cm in length, 6.2 cm in width and 4 cm in height with filter paper (No. 2 manufactured by ADVANTEC), and fix the four corners with a stapler. A 50 g sample is placed, and the following pass rate is determined for the caking state after standing for 28 days in an atmosphere of temperature 30 ° C. and humidity 70% RH.

<Passing rate>
The sample after the test is gently opened on a sieve (mesh opening 4760 μm defined in JIS Z 8801), the weight of the powder that has passed through is measured, and the passage rate (%) with respect to the sample after the test is obtained.

(6) The stain-extracting property is preferably evaluated by the following test method. If tank 1 or rank 2, more preferably rank 1, adhesion of powder containing a nonionic surfactant to equipment in a transport system This is preferable because it is not necessary to devise prevention and prevention of stains on the container.

  Test method for spotting property: Visually evaluate the spotting condition at the bottom of the filter paper container (non-contact surface with powder) when stored for 28 days in the same manner as the caking resistance test. Evaluation is determined by the wetted area of the bottom, and the following 1 to 5 ranks are used.

Rank 1: not wet.
Rank 2: The surface of about 1/4 is wet.
Rank 3: about 1/2 surface is wet.
Rank 4: The surface of about 3/4 is wet.
Rank 5: The entire surface is wet.

Example 1
100 parts by weight of nonion (c-1) was mixed with an anion aqueous solution (54 parts by weight as anion (a-2)), 3.5 parts by weight of PEG and 2.9 parts by weight of mirabilite to obtain a surface activity. An agent composition was prepared. An anion aqueous solution having an effective content of 63% was used. The water content in the surfactant composition was 32 parts by mass with respect to 100 parts by mass of nonion (c-1). Table 1 shows the viscosities of the obtained surfactant composition at 60 ° C, 70 ° C, and 80 ° C.

Example 2
A surfactant composition was prepared in the same manner as in Preparation Example 1, except that the anion (a-1) and the anion (b-1) were used instead of the anion (a-2). Table 1 shows the viscosities of the obtained surfactant composition at 60 ° C, 70 ° C, and 80 ° C.

Comparative Example 1
Except for using nonion (c'-1) instead of nonion (c-1) and using anion (a-1) and anion (b-1) instead of anion (a-2) A surfactant composition was prepared in the same manner as in Preparation Example 1. Table 1 shows the viscosities of the obtained surfactant composition at 60 ° C, 70 ° C, and 80 ° C.

In Examples and Comparative Examples, the following components were used, and are shown in Table 1 with abbreviations.
Anion (a-1): alkyl sulfate sodium salt (carbon number of alkyl group: C14)
Anion (a-2): alkyl sulfate sodium salt (carbon number of alkyl group: C12 / C14)
Anion (b-1): alkyl ether sulfate ester sodium salt (carbon number of alkyl group: C12 / C14, EO average added mole number: 2 mole, PO average added mole number: 0 mole), EMAL 270J manufactured by Kao Corporation
Nonion (c-1): Nonionic surfactant represented by general formula (I):
R ¹ O— (EO) p ₁ (PO) q ₁ (EO) p ₂ H (I)
[Wherein R ¹ is a linear alkyl group having 12 to 14 carbon atoms, EO is an ethyleneoxy group, PO is a propyleneoxy group, p ₁ = 9, q ₁ = 2 and p ₂ = 9 Is the number of Nonion (c′-1): polyoxyethylene alkyl ether (carbon number of alkyl group: C12, EO average addition mole number: 6 mol), Emulgen 108 manufactured by Kao Corporation
PEG: polyethylene glycol (mass average molecular weight: 1,300), XG1300 manufactured by Kao Corporation

  From Table 1, Example 1 and Example 2 using nonion (c-1) differed from Comparative Example 1 using nonion (c'-1), and the ratio of water / (c) was 0.32 Even in this case, it was found that the surfactant composition at a low temperature (60 ° C.) can be kept at a low viscosity that can be handled. On the other hand, in Comparative Example 1, it is considered that a dehydration step was necessary for easier handling.

  The results of analyzing the surfactant compositions of Example 2 and Comparative Example 1 using a two-dimensional image X-ray diffractometer PINT PAPID (Rigaku Corporation) at 60 ° C. are shown in FIG. In the surfactant composition of Example 2, no clear peak was observed between 2θ = 1.5 and 3.0. On the other hand, in the surfactant composition of Comparative Example 1, a peak with an intensity ratio of about 2.0 with respect to the baseline was detected around 2θ = 2.4. From this result, it can be inferred that some structure is formed in the surfactant composition of Comparative Example 1 and the viscosity is increased by the structure.

Example 3 and Comparative Example 2
A detergent composition was prepared according to the following procedure.
(1) Base granules used in step (A) were prepared as follows.
After 410 parts by mass of water was added to the mixing tank and the water temperature reached 45 ° C., 110 parts by mass of sodium sulfate (anhydrous neutral sodium sulfate manufactured by Shikoku Kasei Co., Ltd.), sodium sulfite (manufactured by Mitsui Chemicals, sodium sulfite) 8 2 parts by mass of a fluorescent dye (manufactured by Ciba Specialty Chemicals, Inc., Cinopearl CBS-X) was added and stirred for 10 minutes. Add 120 parts by mass of sodium carbonate (Central Glass Co., Ltd., dense ash, average particle size: 290 μm), and add 150 parts by mass of 40% sodium polyacrylate aqueous solution (Made by Kao Corporation, mass average molecular weight 10,000). Stir for 10 minutes, and add 40 parts by weight of sodium chloride (Nankai Salt Industry Co., Ltd., Nakuru N) and 160 parts by weight of zeolite (ZEOBUILDER, Zeobuilder, 4A type, average particle size: 3.5 μm), The mixture was stirred for 15 minutes to obtain a homogeneous slurry (slurry moisture 50%, temperature 50 ° C.).

  The slurry was supplied to a spray drying tower (counterflow type) with a pump, and sprayed at a spray pressure of 2.5 MPa from a pressure spray nozzle installed near the top of the tower. The hot gas supplied to the spray-drying tower was supplied from the bottom of the tower at a temperature of 285 ° C. and discharged from the top of the tower at 98 ° C. The obtained base granule had a water content of 0.0%, a bulk density of 510 g / L, and an average particle size of 290 μm. For 100 parts by mass of the obtained base granule, 4 parts by mass of silicate (crystalline sodium silicate (pre-feed 6N manufactured by Tokuyama Siltech Co., Ltd., used at an average particle size of 10 μm)), sodium carbonate ( (Average particle size: 290 μm), 26 parts by mass of Central Glass Co., Ltd. soda ash), 9 parts by mass of powdered bentonite (Odosolve K-400 manufactured by Kurosaki Shirato Kogyo Co., Ltd.) and mixed until uniform. Body material was obtained.

(2) The powder raw material and the surfactant composition were mixed as follows, and the surfactant composition was supported on the powder raw material. Here, the surfactant composition used in Example 3 was obtained in Example 1, and the surfactant composition used in Comparative Example 2 was obtained in Comparative Example 1. It was.

  Step (A): 100 parts by mass of the powder raw material was loaded with 38 parts by mass of the surfactant composition. A ribbon mixer (manufactured by Hosokawa Micron: 80 L scale) was used as the carrier, and the temperature of the powder raw material was 60 ° C., the temperature of the surfactant composition was 60 ° C., and the temperature of the warm water jacket of the carrier was 60 ° C.

  Step (B): The detergent composition obtained in Step (A) is transferred to a reformer, and 1.2 parts by mass of fatty acid (alkyl group having 12 to 18 carbon atoms) and polyethylene per 100 parts by mass of the detergent composition. 1.2 parts by weight of glycol was added and mixed until uniform. Subsequently, in order to modify the surface of the detergent composition, 11 parts by mass of zeolite (average particle size: 3.5 μm, manufactured by ZEOBUILDER, Zeobuilder, 4A type) was added as a fine powder. A Redige mixer (Matsuzaka Trading Co., Ltd .: FM130D type: 130L scale) was used as the reformer. The temperature when adding the fine powder was 60 ° C. The modification time after the addition of the fine powder was 1 minute in both Example 3 and Comparative Example 2.

  Table 2 shows the physical properties of the detergent compositions obtained in Example 3 and Comparative Example 2.

  From Table 2, in Comparative Example 2, the low-temperature dissolution rate is 80% or less, and the low-temperature dispersibility is III, which is a state in which aggregates remain, and has a sufficient quality level with respect to solubility and dispersibility at low temperatures. A detergent composition could not be produced.

  On the other hand, for Example 3, a powder detergent composition having sufficient levels of solubility and dispersibility at low temperatures could be produced. In addition, the storage stability was excellent. This is considered to be due to the fact that the surfactant composition has a low viscosity and is efficiently loaded onto the base granule as a powder raw material.

  According to the present invention, a surfactant composition containing an alkyl sulfate that can be handled at a low temperature can be provided. By using such a surfactant composition, it is possible to provide a detergent composition having excellent solubility at low temperatures and low temperature dispersibility.

Claims (7)

A surfactant composition comprising the following components (a) to (d), wherein the amount of the component (d) is such that the surfactant composition does not form a structure at 60 ° C. And having a step of supporting a surfactant composition having a viscosity at 60 ° C. of 0.8 Pa · s or less on a powder raw material in the range of 40 to 70 ° C., an average particle size of 150 to 500 μm, and a bulk density of 500 g The manufacturing method of the detergent composition which is more than / L.
(A): 5-50 mass% of alkyl sulfate,
(B): The following general formula (1):
RO - _{[(PO) m / (EO)} n ] -SO ₃ M (1)
(In the formula, R is a hydrocarbon group, PO and EO are a propyleneoxy group and an ethyleneoxy group, respectively, m and n are the average added moles of PO and EO, respectively, and 0 ≦ m ≦ 5 and 0 <n ≦ 5, “/” is a symbol indicating that the bonding mode of PO and EO may be random addition or block addition, and M is a cation.) 0-50 mass% of sulfate ester salt,
(C): After adding p ₁ mol of ethylene oxide to 1 mol of the compound represented by the formula: R ¹ OH (R ¹ is a hydrocarbon group having 8 to 18 carbon atoms), the number of carbon atoms is 3 A nonionic surfactant obtained by adding ₁ mol of alkylene oxide of ˜5 and then adding ₂ mol of ethylene oxide , wherein p ₁ is a number from 3 to 30, and p ₂ is 1 40 to 70% by mass of a nonionic surfactant having the above number, q ₁ being a number of ₁ to 5, and p ₁ + p ₂ = 16 to 50, and
(D): Water The manufacturing method of Claim 1 whose sum total of the quantity of a component (a) and a component (b) is 10-50 mass% of surfactant composition. The manufacturing method of Claim 1 or 2 whose ratio [(d) / (c)] of a component (d) and a component (c) is 0.01-0.7 (mass ratio). The ratio [(d) / ((a) + (b))] of the component (d) to the total amount of the component (a) and the component (b) is 0.3 to 1.3 (mass ratio). The manufacturing method of any one of Claims 1-3. A surfactant composition comprising the following components (a) to (d), wherein the ratio ((d) / (c)) of component (d) to component (c) is 0.01 to 0.7 (mass ratio), and the ratio of the component (d) to the total amount of the component (a) and the component (b) [(d) / ((a) + (b))] is 0.3 to 1.3 (mass ratio) and having a step of supporting a surfactant composition having a viscosity at 60 ° C. of 0.8 Pa · s or less on a powder raw material in the range of 40 to 70 ° C. The manufacturing method of the detergent composition which is 150-500 micrometers and whose bulk density is 500 g / L or more.
(A): 5-50 mass% of alkyl sulfate,
(B): The following general formula (1):
RO - _{[(PO) m / (EO)} n ] -SO ₃ M (1)
(In the formula, R is a hydrocarbon group, PO and EO are a propyleneoxy group and an ethyleneoxy group, respectively, m and n are the average added moles of PO and EO, respectively, and 0 ≦ m ≦ 5 and 0 <n ≦ 5, “/” is a symbol indicating that the bonding mode of PO and EO may be random addition or block addition, and M is a cation.) 0-50 mass% of sulfate ester salt,
(C): After adding p ₁ mol of ethylene oxide to 1 mol of the compound represented by the formula: R ¹ OH (R ¹ is a hydrocarbon group having 8 to 18 carbon atoms), the number of carbon atoms is 3 A nonionic surfactant obtained by adding ₁ mol of alkylene oxide of ˜5 and then adding ₂ mol of ethylene oxide , wherein p ₁ is a number from 3 to 30, and p ₂ is 1 40 to 70% by mass of a nonionic surfactant having the above number, q ₁ being a number of ₁ to 5, and p ₁ + p ₂ = 16 to 50, and
(D): Water The manufacturing method of Claim 5 whose sum total of the quantity of a component (a) and a component (b) is 10-50 mass% of surfactant composition. Powder material is a detergent builder, manufacturing process according to any one of claims 1 to 6.

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